Benzoxaphosphole compounds and a process for preparation thereof

Abstract

The present inventors prepared novel benzoxaphosphole compounds and shown a process for the synthesizing these novel compounds. The process of preparing the compounds is simple, transition metal free and gives product with high yield. The synthesized benzoxaphosphole compounds are expected to show potential biological.

Claims

1. A compound selected from 3-(4-Chlorophenyl)-1,1,1-triphenyl-1,3-dihydro-1.sup.5-benzo[c][1,2]oxaphosphole (4a), ##STR00087## 3-(4-Methoxyphenyl)-1,1,1-triphenyl-1,3-dihydro-1.sup.5-benzo[c][1,2]oxaphosphole (4b), ##STR00088## 1,1,1-Triphenyl-3-(p-tolyl)-1,3-dihydro-1.sup.5-benzo[c][1,2]oxaphosphole (4c), ##STR00089## 3-(4-Bromophenyl)-1,1,1-triphenyl-1,3-dihydro-1.sup.5-benzo[c][1,2]oxaphosphole (4d), ##STR00090## 1,1,1,3-Tetraphenyl-1,3-dihydro-1.sup.5-benzo[c][1,2]oxaphosphole (4e), ##STR00091## 3-(4-Fluorophenyl)-1,1,1-triphenyl-1,3-dihydro-1.sup.3-benzo[c][1,2]oxaphosphole (4f), ##STR00092## 1,1,1-Triphenyl-3-(4-(trifluoromethyl)phenyl)-1,3-dihydro-1.sup.5-benzo[c][1,2]oxaphosphole (4g), ##STR00093## Methyl-4-(1,1,1-triphenyl-1,3-dihydro-1.sup.5-benzo[c][1,2]oxaphosphol-3-yl) benzoate (4h), ##STR00094## 4-(1,1,1-Triphenyl-1,3-dihydro-1.sup.5-benzo[c][1,2]oxaphosphol-3-yl)benzonitrile (4i), ##STR00095## 3-(3-Methoxyphenyl)-1,1,1-triphenyl-1,3-dihydro-1.sup.5-benzo [c][1,2]oxaphosphole (4j), ##STR00096## 3-(3-Bromophenyl)-1,1,1-triphenyl-1,3-dihydro-1.sup.5-benzo[c][1,2]oxaphosphole (4k), ##STR00097## 3-(3-Nitrophenyl)-1,1,1-triphenyl-1,3-dihydro-1.sup.5-benzo[c][1,2]oxaphosphole (4l), ##STR00098## 1,1,1-Triphenyl-3-(o-tolyl)-1,3-dihydro-1.sup.5-benzo[c][1,2]oxaphosphole (4m), ##STR00099## 3-(2-Fluorophenyl)-1,1,1-triphenyl-1,3-dihydro-1.sup.5-benzo[c][1,2]oxaphosphole (4n), ##STR00100## 3-(3,4-Dichlorophenyl)-1,1,1-triphenyl-1, 3-dihydro-1.sup.5-benzo[c][1,2]oxaphosphole (4o), ##STR00101## 3-Mesityl-1,1,1-triphenyl-1,3-dihydro-1.sup.5-benzo[c][1,2]oxaphosphole (4p), ##STR00102## 3-(Naphthalen-2-yl)-1,1,1-triphenyl-1,3-dihydro-1.sup.5-benzo[c][1,2]oxaphosphole (4q), ##STR00103## 1,1,1-Triphenyl-3-(pyren-4-yl)-1,3-dihydro-1.sup.5-benzo[c][1,2]oxaphosphole (4r), ##STR00104## 3-(Benzofuran-2-yl)-1,1,1-triphenyl-1,3-dihydro-1.sup.5-benzo[c][1,2]oxaphosphole (4s), ##STR00105## 1,1,1-Triphenyl-3-(thiophen-2-yl)-1,3-dihydro-1.sup.5-benzo[c][1,2]oxaphosphole (4t), ##STR00106## 3-Cyclohexyl-1,1,1-triphenyl-1,3-dihydro-1.sup.5-benzo[c][1,2]oxaphosphole (4u), ##STR00107## 3-Nonyl-1,1,1-triphenyl-1,3-dihydro-1.sup.5-benzo[c][1,2]oxaphosphole (4v), ##STR00108## 1,1,1-Triphenyl-3-vinyl-1,3-dihydro-1.sup.5-benzo[c][1,2]oxaphosphole (4w), ##STR00109## 1,1,1-Triphenyl-3-styryl-1,3-dihydro-1.sup.5-benzo[c][1,2]oxaphosphole (4x), ##STR00110## 3-(4-Methoxystyryl)-1,1,1-triphenyl-1,3-dihydro-1.sup.5-benzo[c][1,2]oxaphosphole (4y), ##STR00111## 3-(4-Chlorophenyl)-5,6-dimethyl-1,1,1-triphenyl-1,3-dihydro-1.sup.5benzo[c][1,2]oxaphosphole (4z), ##STR00112## 3-(4-Chlorophenyl)-5,6-difluoro-1,1,1-triphenyl-1,3-dihydro-1.sup.5-benzo[c][1,2]oxaphosphole (4aa), ##STR00113## 3-(4-Chlorophenyl)-1,1,1-triphenyl-1,3-dihydro-1.sup.5-[1,3]dioxolo[4,5:4,5]benzo[1,2-c][1,2]oxaphosphole (4ab), ##STR00114## 3-(4-Chlorophenyl)-1,1,1-triphenyl-3,5,6,7-tetrahydro-1H-1.sup.5-indeno[5,6-c][1,2]oxaphosphole (4ac), ##STR00115## 1-(4-Chlorophenyl)-3,3,3-triphenyl-1,3-dihydro-3.sup.3-naphtho[2,1-c][1,2]oxaphosphole (4ad), ##STR00116## 3-(4-Chlorophenyl)-5-methyl-1,1,1-triphenyl-1,3-dihydro-1.sup.5-benzo[c][1,2]oxaphosphole (4ae) ##STR00117## 3-(4-Chlorophenyl)-6-methyl-1,1,1-triphenyl-1,3-dihydro-1.sup.5-benzo[c][1,2]oxaphosphole (4ae) ##STR00118## 3-(4-Chlorophenyl)-5-fluoro-1,1,1-triphenyl-1,3-dihydro-1.sup.5-benzo[c][1,2]oxaphosphole (4af), ##STR00119## 3-(4-Chlorophenyl)-6-fluoro-1,1,1-triphenyl-1,3-dihydro-1.sup.5-benzo[c][1,2]oxaphosphole (4af), ##STR00120## 3-(4-Chlorophenyl)-1,1,1-tri-p-tolyl-1,3-dihydro-1.sup.5-benzo[c][1,2]oxaphosphole (4ag), ##STR00121## 3-(4-Chlorophenyl)-1,1,1-tris(4-methoxyphenyl)-1,3-dihydro-1.sup.5-benzo[c][1,2]oxaphosphole (4ah), ##STR00122## 3-(4-Chlorophenyl)-1,1,1-tri-o-tolyl-1,3-dihydro-1.sup.5-benzo[c][1,2]oxaphosphole (4ai), ##STR00123## 3-(4-Chlorophenyl)-1,1-diphenyl-1-(p-tolyl)-1,3-dihydro-1.sup.5-benzo[c][1,2]oxaphosphole (4aj) ##STR00124## and 1,1,1-Tributyl-3-(4-chlorophenyl)-1,3-dihydro-1.sup.5-benzo[c][1,2]oxaphosphole (4ak) ##STR00125##

2. A process for preparing a compound of claim 1, wherein the process comprises the steps of: a) cooling a reaction mixture of 18-crown-6, KF and a phosphine precursor in THF at 10 C. to 0 C. followed by stirring for 5-10 minutes; b) adding an aryne precursor to the reaction mixture of step (a) followed by continued stirring for an additional 5-10 minutes at 10 C. to 0 C.; c) adding an aldehyde to the reaction mixture of step (b) and continued stirring from 10 C. to room temperature for 12 h-15 h to obtain a compounds of claim 1, wherein room temperature is from 25-35 C.

3. The process as claimed in claim 2, wherein the process is carried out under an argon atmosphere.

4. The process as claimed in claim 2, wherein the aryne precursors are selected from trimethylsilyl triflates optionally substituted with one or two substituents each of which is independently selected from alkyl, halogen, alkoxy, haloalkyl, cyano, nitro, hydroxy, aryl, naphthyl, phenanthryl and may optionally form carbocyclic ring or heterocyclic ring containing one or more heteroatoms selected from the group consisting of: O, N.

5. The process as claimed in claim 4, wherein the aryne precursors are selected from 2-(trimethylsilyl)phenyl trifluoromethanesulfonate, 4,5-dimethyl-2-(trimethylsilyl)phenyl trifluoromethanesulfonate, 4,5-difluoro-2-(trimethylsilyl) phenyl trifluoromethanesulfonate, 6-(trimethylsilyl)benzo[d][1,3]dioxol-5-yl trifluoromethanesulfonate, 6-(trimethylsilyl)-2,3-dihydro-1H-inden-5-yl trifluoromethanesulfonate, 2-(trimethylsilyl)naphthalen-1-yl trifluoromethanesulfonate, 5-methyl-2-(trimethylsilyl)phenyl trifluoromethanesulfonate, 4-fluoro-2-(trimethylsilyl)phenyl trifluoromethanesulfonate.

6. The process as claimed in claim 2, wherein the aldehydes are selected from aromatic aldehydes, aliphatic aldehydes, heterocyclic aldehydes; and ,-unsaturated aldehydes.

7. The process as claimed in claim 6, wherein the aldehydes are selected from benzaldehyde, 4-chlorobenzaldehyde, 4-methoxybenzaldehyde, 4-methylbenzaldehyde, 4-bromobenzaldehyde, 4-fluorobenzaldehyde, 4-(trifluoromethyl)benzaldehyde, methyl 4-formylbenzoate, 4-formylbenzonitrile, 3-methoxybenzaldehyde, 3-bromobenzaldehyde, 3-nitrobenzaldehyde, 2-methylbenzaldehyde, 2-fluorobenzaldehyde, 3,4-dichlorobenzaldehyde, 2,4,6-trimethylbenzaldehyde, 2-naphthaldehyde, pyrene-4-carbaldehyde, benzofuran-2-carbaldehyde, thiophene-2-carbaldehyde, cyclohexanecarbaldehyde, decanal, acrylaldehyde, trans cinnamaldehyde, (E)-3-(4-methoxyphenyl)acrylaldehyde.

8. The process as claimed in claim 2, wherein the phosphine precursors are selected from tri-p-tolylphosphane, tris(4-methoxyphenyl)phosphane, tri-o-tolylphosphane, diphenyl (p-tolyl)phosphane, tri-n-butylphosphine.

9. The process as claimed in claim 2, wherein a yield of the compounds of claim 1 is 55-95%.

Description

DETAILED DESCRIPTION OF THE INVENTION

(1) Accordingly, the main embodiment of the present invention provides a compound of formula (I),

(2) ##STR00007##

(3) wherein,

(4) R.sup.1 is selected from hydrogen, alkyl, halogen, OMe, OCH.sub.2O, (CH.sub.2).sub.3, (CH.sub.2).sub.4-naphthyl, phenanthryl;

(5) R.sup.2 is selected from various aromatic aldehydes (electron releasing, electron withdrawing and neutral), aliphatic aldehydes, heterocyclic aldehydes, ,-unsaturated aldehydes; and

(6) R.sup.3, R.sup.4, R.sup.5 are independently selected from aryl, heteroaryl, alkyl phosphines.

(7) In another embodiment of the present invention, wherein the compounds of formula (I) are preferably selected from group comprising, 3-(4-Chlorophenyl)-1,1,1-triphenyl-1,3-dihydro-1.sup.5-benzo [c][1,2]oxaphosphole (4a)

(8) ##STR00008## 3-(4-Methoxyphenyl)-1,1,1-triphenyl-1,3-dihydro-1.sup.5-benzo[c][1,2]oxaphosphole (4b)

(9) ##STR00009## 1,1,1-Triphenyl-3-(p-tolyl)-1,3-dihydro-1.sup.5-benzo[c][1,2] oxaphosphole (4c)

(10) ##STR00010## 3-(4-Bromophenyl)-1,1,1-triphenyl-1,3-dihydro-1.sup.5-benzo [c][1,2]oxaphosphole (4d)

(11) ##STR00011## 1,1,1,3-Tetraphenyl-1,3-dihydro-1.sup.5-benzo[c][1,2] oxaphosphole (4e)

(12) ##STR00012## 3-(4-Fluorophenyl)-1,1,1-triphenyl-1,3-dihydro-1.sup.5-benzo [c][1,2]oxaphosphole (4f)

(13) ##STR00013## 1,1,1-Triphenyl-3-(4-(trifluoromethyl)phenyl)-1,3-dihydro-1.sup.5-benzo[c][1,2] oxaphosphole (4g)

(14) ##STR00014## Methyl-4-(1,1,1-triphenyl-1,3-dihydro-1.sup.5-benzo[c][1,2] oxaphosphol-3-yl) benzoate (4h)

(15) ##STR00015## 4-(1,1,1-Triphenyl-1,3-dihydro-1.sup.5-benzo[c][1,2] oxaphosphol-3-yl)benzonitrile (4i)

(16) ##STR00016## 3-(3-Methoxyphenyl)-1,1,1-triphenyl-1,3-dihydro-1.sup.5-benzo [c][1,2]oxaphosphole (4j)

(17) ##STR00017## 3-(3-Bromophenyl)-1,1,1-triphenyl-1,3-dihydro-1.sup.5-benzo[c][1,2]oxaphosphole (4k)

(18) ##STR00018## 3-(3-Nitrophenyl)-1,1,1-triphenyl-1,3-dihydro-1.sup.5-benzo [c][1,2]oxaphosphole (4l)

(19) ##STR00019## 1,1,1-Triphenyl-3-(o-tolyl)-1,3-dihydro-1.sup.5-benzo[c][1,2]oxaphosphole (4m)

(20) ##STR00020## 3-(2-Fluorophenyl)-1,1,1-triphenyl-1,3-dihydro-1.sup.5-benzo [c][1,2]oxaphosphole (4n)

(21) ##STR00021## 3-(3,4-Dichlorophenyl)-1,1,1-triphenyl-1,3-dihydro-1.sup.5-benzo[c][1,2]oxaphosphole (4o)

(22) ##STR00022## 3-Mesityl-1,1,1-triphenyl-1,3-dihydro-1.sup.5-benzo[c][1,2]oxaphosphole (4p)

(23) ##STR00023## 3-(Naphthalen-2-yl)-1,1,1-triphenyl-1,3-dihydro-1.sup.5-benzo [c][1,2]oxaphosphole (4q)

(24) ##STR00024## 1,1,1-Triphenyl-3-(pyren-4-yl)-1,3-dihydro-1.sup.5-benzo[c] [1,2]oxaphosphole (4r)

(25) ##STR00025## 3-(Benzofuran-2-yl)-1,1,1-triphenyl-1,3-dihydro-1.sup.5-benzo [c][1,2]oxaphosphole (4s)

(26) ##STR00026## 1,1,1-Triphenyl-3-(thiophen-2-yl)-1,3-dihydro-1.sup.5-benzo [c][1,2] oxaphosphole (4t)

(27) ##STR00027## 3-Cyclohexyl-1,1,1-triphenyl-1,3-dihydro-1.sup.5-benzo[c][1,2] oxaphosphole (4u)

(28) ##STR00028## 3-Nonyl-1,1,1-triphenyl-1,3-dihydro-1.sup.5-benzo[c][1,2] oxaphosphole (4v)

(29) ##STR00029## 1,1,1-Triphenyl-3-vinyl-1,3-dihydro-1.sup.5-benzo[c][1,2] oxaphosphole (4w)

(30) ##STR00030## 1,1,1-Triphenyl-3-styryl-1,3-dihydro-1.sup.5-benzo[c][1,2] oxaphosphole (4x)

(31) ##STR00031## 3-(4-Methoxystyryl)-1,1,1-triphenyl-1,3-dihydro-1.sup.5-benzo[c][1,2]oxaphosphole (4y)

(32) ##STR00032## 3-(4-Chlorophenyl)-5,6-dimethyl-1,1,1-triphenyl-1,3-dihydro-1.sup.5 benzo[c][1,2]oxaphosphole (4z)

(33) ##STR00033## 3-(4-Chlorophenyl)-5,6-difluoro-1,1,1-triphenyl-1,3-dihydro-1.sup.5-benzo[c][1,2] oxaphosphole (4aa)

(34) ##STR00034## 3-(4-Chlorophenyl)-1,1,1-triphenyl-1,3-dihydro-1.sup.5[1,3]dioxolo [4,5:4,5]benzo [1,2-c][1,2]oxaphosphole (4ab)

(35) ##STR00035## 3-(4-Chlorophenyl)-1,1,1-triphenyl-3,5,6,7-tetrahydro-1H-1.sup.5-indeno[5,6-c][1,2]oxaphosphole (4ac)

(36) ##STR00036## 1-(4-Chlorophenyl)-3,3,3-triphenyl-1,3-dihydro-3.sup.5-naphtho[2,1-c][1,2]oxaphosphole (4ad)

(37) ##STR00037## 3-(4-Chlorophenyl)-5-methyl-1,1,1-triphenyl-1,3-dihydro-1.sup.5-benzo[c][1,2] oxaphosphole (4ae)

(38) ##STR00038## 3-(4-Chlorophenyl)-6-methyl-1,1,1-triphenyl-1,3-dihydro-1.sup.5-benzo[c][1,2] oxaphosphole (4ae)

(39) ##STR00039## 3-(4-Chlorophenyl)-5-fluoro-1,1,1-triphenyl-1,3-dihydro-1.sup.5-benzo [c][1,2]oxaphosphole (4af)

(40) ##STR00040## 3-(4-Chlorophenyl)-6-fluoro-1,1,1-triphenyl-1,3-dihydro-1.sup.5-benzo[c][1,2]oxaphosphole (4af)

(41) ##STR00041## 3-(4-Chlorophenyl)-1,1,1-tri-p-tolyl-1,3-dihydro-1.sup.5-benzo[c][1,2]oxaphosphole (4ag)

(42) ##STR00042## 3-(4-Chlorophenyl)-1,1,1-tris(4-methoxyphenyl)-1,3-dihydro-1.sup.5-benzo[c] [1,2]oxaphosphole (4ah)

(43) ##STR00043## 3-(4-Chlorophenyl)-1,1,1-tri-o-tolyl-1,3-dihydro-1.sup.5-benzo[c][1,2]oxaphosphole (4ai)

(44) ##STR00044## 3-(4-Chlorophenyl)-1,1-diphenyl-1-(p-tolyl)-1,3-dihydro-1.sup.5-benzo[c][1,2]oxaphosphole (4aj)

(45) ##STR00045## 1,1,1-Tributyl-3-(4-chlorophenyl)-1,3-dihydro-1.sup.5-benzo[c] [1,2]oxaphosphole (4ak)

(46) ##STR00046##

(47) Another embodiment of the present invention provides a process for the preparation of benzoxaphosphole compounds of formula (I), wherein the process comprising the steps of:

(48) cooling the reaction mixture of 18-crown-6, KF and phosphine precursor in THF at 10 C. to 0 C. followed by stirring for 5-10 minutes;

(49) adding aryne precursor to the reaction mixture of step (a) followed continued stirring for additional 5-10 minutes at 10 C. to 0 C.;

(50) adding aldehyde to the reaction mixture of step (b) and continued stirring from 10 C. to room temperature (25-35 C.) for 12 h-15 h to obtain the compounds of formula (I).

(51) a. In another embodiment of the present invention, wherein the reaction is carried out under argon atmosphere.

(52) b. In another embodiment of the present invention, wherein the aryne precursors are selected from trimethylsilyl triflates optionally substituted with one or two substituents each of which is independently selected from alkyl, halogen, alkoxy, haloalkyl, cyano, nitro, hydroxy, aryl, naphthyl, phenanthryl and may optionally form carbocyclic ring or heterocyclic ring containing one or more heteroatoms selected from the group consisting of: O, N.
c. In another embodiment of the present invention, wherein the aryne precursors are preferably selected from 2-(trimethylsilyl)phenyl trifluoromethanesulfonate, 4,5-dimethyl-2-(trimethylsilyl)phenyl trifluoromethanesulfonate, 4,5-difluoro-2-(trimethylsilyl) phenyl trifluoromethanesulfonate, 6-(trimethylsilyl)benzo[d][1,3]dioxol-5-yl trifluoromethanesulfonate, 6-(trimethylsilyl)-2,3-dihydro-1H-inden-5-yl trifluoro-methanesulfonate, 2-(trimethylsilyl)naphthalen-1-yl trifluoromethanesulfonate, 5-methyl-2-(trimethylsilyl)phenyl trifluoromethanesulfonate, 4-fluoro-2-(trimethylsilyl)phenyl trifluoromethanesulfonate.
d. In another embodiment of the present invention, wherein the aldehydes are selected from aromatic aldehydes, aliphatic aldehydes, heterocyclic aldehydes, ,-unsaturated aldehydes.
e. In another embodiment of the present invention, wherein the aldehydes are preferably selected from benzaldehyde, 4-chlorobenzaldehyde, 4-methoxybenzaldehyde, 4-methylbenzaldehyde, 4-bromobenzaldehyde, 4-fluorobenzaldehyde, 4-(trifluoromethyl)benzaldehyde, methyl 4-formylbenzoate, 4-formylbenzonitrile, 3-methoxybenzaldehyde, 3-bromobenzaldehyde, 3-nitrobenzaldehyde, 2-methylbenzaldehyde, 2-fluorobenzaldehyde, 3,4-dichlorobenzaldehyde, 2,4, 6-trimethylbenzaldehyde, 2-naphthaldehyde, pyrene-4-carbaldehyde, benzofuran-2-carbaldehyde, thiophene-2-carbaldehyde, cyclohexanecarbaldehyde, decanal, acrylaldehyde, trans cinnamaldehyde, (E)-3-(4-methoxyphenyl)acrylaldehyde.
f. In another embodiment of the present invention, wherein phosphine precursors are preferably selected from tri-p-tolylphosphane, tris(4-methoxyphenyl)phosphane, tri-o-tolylphosphane, diphenyl (p-tolyl)phosphane, tri-n-butylphosphine.
g. In another embodiment of the present invention, wherein yield of benzoxaphosphole compounds of formula (I) is in the range of 55-95%.

(53) Further, the present invention provides a process for the preparation of novel benzoxaphosphole compounds of formula (I) comprising the step of:

(54) cooling the predation mixture of 18-crown-6, KF and phosphine precursor in THF at 10 C. followed by stirring for 5 minutes;

(55) adding aryne precursor to the reaction mixture of step (a) followed continued stirring for additional 5 minutes at 10 C.;

(56) adding aldehyde to the reaction mixture of step (b) and continued stirring from 10 C. to room temperature for 12 h to afford the compounds of formula (I);

(57) a. Wherein, the reaction is carried out under argon atmosphere.

(58) The process for preparation of novel benzoxaphosphole compounds of Formula (I) is as shown below in Scheme 1:

(59) ##STR00047##

(60) The aryne precursor are selected from trimethylsilyl triplanes optionally substituted with one or two substituents each of which is independently selected from alkyl, halogen, alkoxy, haloalkyl, cyano, nitro, hydroxy, aryl, naphthyl, phenanthryl and may optionally form carbocyclic ring or heterocyclic ring containing one or more heteroatoms selected from the group consisting of: O, N.

(61) The aryne precursors used for the preparation of novel benzoxaphosphole compounds of formula (I) are preferably selected from 2-(trimethylsilyl)phenyl trifluoromethanesulfonate, 4,5-dimethyl-2-(trimethylsilyl)phenyl trifluoromethanesulfonate, 4,5-difluoro-2-(trimethylsilyl) phenyl trifluoromethane-sulfonate, 6-(trimethylsilyl)benzo[d] [1,3]dioxol-5-yl trifluoromethanesulfonate, 6-(trimethylsilyl)-2,3-dihydro-1H-inden-5-yl trifluoro-methanesulfonate, 2-(trimethylsilyl) naphthalen-1-yl trifluoromethanesulfonate, 5-methyl-2-(trimethylsilyl)phenyl trifluoro-methanesulfonate, 4-fluoro-2-(trimethylsilyl)phenyl trifluoromethanesulfonate.

(62) The aldehyde are selected from aromatic aldehydes, aliphatic aldehydes, heterocyclic aldehydes, ,-unsaturated aldehydes.

(63) The aldehydes used for the preparation of novel benzoxaphosphole compounds of formula (I) are preferably selected from benzaldehyde, 4-chlorobenzaldehyde, 4-methoxybenzaldehyde, 4-methylbenzaldehyde, 4-bromobenzaldehyde, 4-fluorobenzaldehyde, 4-(trifluoromethyl)benzaldehyde, methyl 4-formylbenzoate, 4-formylbenzonitrile, 3-methoxybenzaldehyde, 3-bromobenzaldehyde, 3-nitrobenzaldehyde, decanal, 2-methylbenzaldehyde, 2-fluorobenzaldehyde, 3,4-dichlorobenzaldehyde, 2,4,6-trimethylbenzaldehyde, 2-naphthaldehyde, pyrene-4-carbaldehyde, benzofuran-2-carbaldehyde, acrylaldehyde, thiophene-2-carbaldehyde, cyclohexanecarbaldehyde, trans cinnamaldehyde, (E)-3-(4-methoxyphenyl) acrylaldehyde.

(64) The phosphine precursors used for the preparation of novel benzoxaphosphole compounds of formula (I) are preferably selected from tri-p-tolylphosphane, tris(4-methoxyphenyl)phosphane, tri-o-tolylphosphane, diphenyl (p-tolyl)phosphane, tri-n-butylphosphine.

(65) In an aspect, the present invention provides a process for the preparation of novel benzoxaphosphole compounds of formula (I) wherein the reaction proceeds via the initial generation of a 1,3-zwitterionic intermediate from phosphine and aryne, which undergoes a formal [3+2] cycloaddition with aldehydes allowing the synthesis of phosphorus heterocycles

(66) The present invention provides a process for the preparation of novel benzoxaphosphole compounds of formula (I) wherein the ratio of each reactant is shown below:

(67) ##STR00048##

EXAMPLES

(68) The following examples are given by way of illustration only and therefore should not be construed to limit the scope of the present invention.

(69) General procedure for preparation of compound of formula (I):

(70) ##STR00049##

(71) To a flame-dried screw-capped Schlenk tube equipped with a magnetic stir bar was added 18-crown-6 (0.634 g, 2.40 mmol), KF (Potassium fluoride) (0.140 g, 2.40 mmol) and triphenyl phosphine 1c (1.0 mmol). Then the screw-capped tube was evacuated and backfilled with argon. The mixture was dissolved in THF (6.0 mL) under argon atmosphere and cooled to 10 C. and continued stirring for 5 minutes. To the stirring solution was added the aryne precursor 1a and continued stirring for additional 5 minutes at 10 C. Finally added the aldehyde 1b to the reaction mixture and continued stirring from 10 C. to room temperature for 12 h. Then the crude reaction mixture was purified by column chromatography on silica gel to afford the corresponding product.

Example 1: Synthesis of 3-(4-Chlorophenyl)-1,1,1-triphenyl-1,3-dihydro-15-benzo [c][1,2]oxaphosphole (4a)

(72) ##STR00050##

(73) Following the general procedure, treatment of 2-(trimethylsilyl)phenyl trifluoromethanesulfonate 1a (0.358 g, 292 L, 1.20 mmol) and 4-chlorobenzaldehyde 1b (0.211 g, 1.50 mmol) with triphenylphosphine 1c (0.262 g, 1.0 mmol) in the presence of KF (0.140 g, 2.40 mmol) and 18-crown-6 (0.634 g, 2.40 mmol) in THF (6.0 mL) at ()10 C. to rt for 12 h followed by flash column chromatography (Pet. ether/EtOAc=40/60) of the crude reaction mixture using silica gel afforded 3-(4-chlorophenyl)-1,1,1-triphenyl-1,3-dihydro-1.sup.5-benzo[c][1,2]oxaphosphole 4a as a white solid (0.389 g, 81% yield).

(74) R.sub.f (EtOAc): 0.41; .sup.1H NMR (500 MHz, CDCl.sub.3) 7.47 (t, J=6.6 Hz, 1H, H.sub.ar), 7.41-7.37 (m, 6H, H.sub.ar), 7.35-7.31 (m, 9H, H.sub.ar), 7.23-7.20 (m, 4H, H.sub.ar), 7.08 (d, J=7.9 Hz, 2H, H.sub.ar), 6.87 (t, J=10.7 Hz, 1H, H.sub.ar), 5.60 (s, 1H, CH). .sup.13C NMR (125 MHz, CDCl.sub.3) 153.92 (d, J=21.5 Hz), 143.72, 142.93, 136.56 (d, J=21.5 Hz), 132.95, 132.31 (d, J=2.4 Hz), 131.42 (d, J=8.8 Hz), 129.16, 129.02, 128.38, 128.13, 127.96, 127.53, 127.43, 127.36, 124.77 (d, J=15.4 Hz), 76.25. .sup.31P NMR (203 MHz, CDCl.sub.3) 51.41 HRMS (ESI) calculated [M+H].sup.+ for C.sub.31H.sub.25ClOP: 479.1326. found: 479.1327. FTIR (cm.sup.1) 3829, 3743, 3618, 3058, 3005, 1897, 1588, 1485, 1437, 1406, 1257, 1229, 1183, 1112, 1078, 1020, 886, 847, 745, 695, 663.

Example 2: Synthesis of 3-(4-Methoxyphenyl)-1,1,1-triphenyl-1,3-dihydro-15-benzo[c][1,2] oxaphosphole (4b)

(75) ##STR00051##

(76) Following the general procedure, treatment of 2-(trimethylsilyl)phenyl trifluoromethanesulfonate 1a (0.179 g, 146 L, 0.60 mmol) and 4-methoxybenzaldehyde 1b (0.102 g, 91 L, 0.75 mmol) with triphenylphosphine 1c (0.131 g, 0.50 mmol) in the presence of KF (0.070 g, 1.20 mmol) and 18-crown-6 (0.317 g, 1.20 mmol) in THF (3.0 mL) at 10 C. to rt for 12 h followed by flash column chromatography (Pet. ether/EtOAc=40/60) of the crude reaction mixture using silica gel afforded 3-(4-methoxyphenyl)-1,1,1-triphenyl-1,3-dihydro-1.sup.5-benzo[c][1,2]oxaphosphole 4b as a white solid (0.182 g, 77% yield).

(77) R.sub.f (EtOAc): 0.38; .sup.1H NMR (400 MHz, CDCl.sub.3) 7.49-7.46 (m, 1H, H.sub.ar), 7.42-7.39 (m, 6H, H.sub.ar), 7.33-7.29 (m, 9H, H.sub.ar), 7.23 (t, J=5.8 Hz, 2H, H.sub.ar), 7.11 (d, J=8.4 Hz, 2H, H.sub.ar), 6.86-6.81 (m, 3H, H.sub.ar), 5.52 (s, 1H, CH), 3.79 (s, 3H, CH.sub.3). .sup.13C NMR (100 MHz, CDCl.sub.3) 158.98, 154.88 (d, J=21.6 Hz), 144.17, 143.11, 136.46 (d, J=6.5 Hz), 136.28, 132.15 (d, J=3.1 Hz), 131.59 (d, J=8.9 Hz), 129.12, 128.03, 127.41 (d, J=12.3 Hz), 127.26, 127.12, 124.90 (d, J=15.4 Hz), 113.69, 76.23, 55.32. .sup.31P NMR (162 MHz, CDCl.sub.3) 52.65. HRMS (ESI) calculated [M+H].sup.+ for C.sub.32H.sub.28O.sub.2P: 475.1821. found: 475.1822. FTIR (cm.sup.1) 3843, 3649, 3005, 2361, 1836, 1741, 1693, 1647, 1484, 1436, 1246, 1216, 1118, 1050, 742, 699, 665.

Example 3: Synthesis of 1,1,1-Triphenyl-3-(p-tolyl)-1,3-dihydro-15-benzo[c][1,2] oxaphosphole (4c)

(78) ##STR00052##

(79) Following the general procedure, treatment of 2-(trimethylsilyl)phenyl trifluoromethanesulfonate 1a (0.179 g, 146 L, 0.6 mmol) and 4-methylbenzaldehyde 1b (0.090 g, 88 L, 0.75 mmol) with triphenylphosphine 1c (0.131 g, 0.5 mmol) in the presence of KF (0.070 g, 1.20 mmol) and 18-crown-6 (0.317 g, 1.20 mmol) in THF (3.0 mL) at 10 C. to rt for 12 h followed by flash column chromatography (Pet. ether/EtOAc=40/60) of the crude reaction mixture using silica gel afforded 1,1,1-triphenyl-3-(p-tolyl)-1,3-dihydro-1.sup.5-benzo[c][1,2]oxaphosphole 4c as a white solid (0.154 g, 67% yield).

(80) R.sub.f (EtOAc): 0.44; .sup.1H NMR (500 MHz, CDCl.sub.3) 7.44 (t, J=6.2 Hz, 1H, H.sub.ar), 7.39-7.35 (m, 6H, H.sub.ar), 7.32-7.27 (m, 9H, H.sub.ar), 7.22 (dd, =6.6 Hz, J.sub.2=13.0 Hz, 2H, H.sub.ar), 7.0-7.03 (m, 4H, H.sub.ar), 6.82 (dd, J.sub.1=8.3 Hz, J.sub.2=10.3 Hz, 1H, H.sub.ar), 5.51 (s, 1H, CH), 2.30 (s, 3H, CH.sub.3). .sup.13C NMR (125 MHz, CDCl.sub.3) 154.75 (d, J=21.8 Hz), 144.06, 143.22, 141.23, 136.83, 136.37 (d, J=14.6 Hz), 132.17 (d, J=2.5 Hz), 131.58 (d, J=9.1 Hz), 128.96, 128.29, 128.0 (d, J=1.8 Hz), 127.26, 127.41 (d, J=12.5 Hz), 127.17 (d, J=14.1 Hz), 124.88 (d, J=15.6 Hz), 76.58. .sup.31P NMR (203 MHz, CDCl.sub.3) 52.08. HRMS (ESI) calculated [M+H].sup.+ for C.sub.32H.sub.28OP: 459.1872. found 459.1872. FTIR (cm.sup.1) 3843, 3013, 2361, 1835, 1647, 1515, 1214, 1033, 742, 666.

Example 4: Synthesis of 3-(4-Bromophenyl)-1,1,1-triphenyl-1,3-dihydro-15-benzo [c] [1,2] oxaphosphole (4d)

(81) ##STR00053##

(82) Following the general procedure, treatment of 2-(trimethylsilyl)phenyl trifluoromethanesulfonate 1a (0.179 g, 146 L, 0.60 mmol) and 4-bromobenzaldehyde 1b (0.137 g, 0.75 mmol) with triphenylphosphine 1c (0.131 g, 0.50 mmol) in the presence of KF (0.070 g, 1.20 mmol) and 18-crown-6 (0.317 g, 1.20 mmol) in THF (3.0 mL) at 10 C. to rt for 12 h followed by flash column chromatography (Pet. ether/EtOAc=40/60) of the crude reaction mixture using silica gel afforded 3-(4-bromophenyl)-1,1,1-triphenyl-1,3-dihydro-1.sup.5-benzo[c][1,2]oxaphosphole 4d as a white solid (0.223 g, 85% yield).

(83) R.sub.f (EtOAc): 0.42; .sup.1H NMR (400 MHz, CDCl.sub.3) 7.46 (t, J=6.4 Hz, 1H, H.sub.ar), 7.37-7.35 (m, 5H, H.sub.ar), 7.33-7.26 (m, 12H, H.sub.ar), 7.23-7.17 (m, 2H, H.sub.ar), 6.98 (d, J=8.3 Hz, 2H, H.sub.ar), 6.84 (dd, J.sub.1=8.2 Hz, J.sub.2=11.2 Hz, 1H, H.sub.ar), 5.56 (s, 1H, CH). .sup.13C NMR (100 MHz, CDCl.sub.3) 153.82 (d, J=21.2 Hz), 143.47, 142.38, 136.63 (d, J=14.5 Hz), 132.41 (d, J=2.7 Hz), 131.52 (d, J=8.8 Hz), 131.35, 129.55, 128.29, 127.56 (d, J=12.3 Hz), 127.40, 124.96 (d, J=14.9 Hz), 121.17, 76.30. .sup.31P NMR (162 MHz, CDCl.sub.3) 51.38 HRMS (ESI) calculated [M+H].sup.+ for C.sub.31H.sub.25BrOP: 523.0821. found: 523.0825. FTIR (cm.sup.1) 3894, 3843, 3743, 3619, 2982. 2360, 1835, 1707, 1615, 1467, 1435, 1249, 1180, 1046, 844, 743, 665.

Example 5: Synthesis of 1,1,1,3-Tetraphenyl-1,3-dihydro-15-benzo[c] [1,2] oxaphosphole (4e)

(84) ##STR00054##

(85) Following the general procedure, treatment of 2-(trimethylsilyl)phenyl trifluoromethanesulfonate 1a (0.179 g, 146 L, 0.60 mmol) and benzaldehyde 1b (0.105 g, 0.75 mmol) with triphenylphosphine 1c (0.080 g, 76 L, 0.50 mmol) in the presence of KF (0.070 g, 1.20 mmol) and 18-crown-6 (0.317 g, 1.20 mmol) in THF (3.0 mL) at 10 C. to rt for 12 h followed by flash column chromatography (Pet. ether/EtOAc=40/60) of the crude reaction mixture using silica gel afforded 1,1,1,3-tetraphenyl-1,3-dihydro-1.sup.5-benzo[c][1,2]oxaphosphole 4e as a white solid (0.180 g, 81% yield).

(86) R.sub.f (EtOAc): 0.40; .sup.1H NMR (400 MHz, CDCl.sub.3) 7.45-7.36 (m, 7H, H.sub.ar), 7.31 (bs, 9H, H.sub.ar), 7.26-7.22 (m, 5H, H.sub.ar), 7.15 (d, J=7.1 Hz, 2H, H.sub.ar), 6.83 (t, J=8.4 Hz, 1H, H.sub.ar), 5.56 (s, 1H, CH). .sup.13C NMR (100 MHz, CDCl.sub.3) 154.44 (d, J=21.4 Hz), 144.17, 143.62 (d, J=12.5 Hz), 142.65, 142.55, 136.46 (d, J=14.5 Hz), 132.27 (d, J=2.3 Hz), 131.64 (d, J=8.8 Hz), 128.28, 128.21, 127.92, 127.57, 127.44, 127.34, 127.21, 125.01 (d, J=15.5 Hz), 76.74. .sup.31P NMR (162 MHz, CDCl.sub.3) 48.23 HRMS (ESI) calculated [M+H].sup.+ for C.sub.31H.sub.26ClOP: 445.1716. found: 445.1718. FTIR (cm.sup.1) 3860, 3677, 3619, 3013, 2362, 1741, 1693, 1647, 1516, 1462, 1216, 1117, 1057, 741, 667, 633.

Example 6: Synthesis of 3-(4-Fluorophenyl)-1,1,1-triphenyl-1,3-dihydro-15-benzo [c][1,2]oxaphosphole (4f)

(87) ##STR00055##

(88) Following the general procedure, treatment of 2-(trimethylsilyl)phenyl trifluoromethanesulfonate 1a (0.179 g, 146 L, 0.6 mmol) and 4-fluorobenzaldehyde 1b (0.093 g, 81 L, 0.75 mmol) with triphenylphosphine 1c (0.131 g, 0.5 mmol) in the presence of KF (0.070 g, 1.2 mmol) and 18-crown-6 (0.317 g, 1.2 mmol) in THF (3.0 mL) at 10 C. to rt for 12 h followed by flash column chromatography (Pet. ether/EtOAc=40/60) of the crude reaction mixture using silica gel afforded 3-(4-fluorophenyl)-1,1,1-triphenyl-1,3-dihydro-1.sup.5-benzo[c][1,2]oxaphosphole 4f as a white solid (0.181 g, 78% yield).

(89) R.sub.f (EtOAc): 0.53; .sup.1H NMR (500 MHz, CDCl.sub.3) 7.49 (t, J=6.5 Hz, 1H, H.sub.ar), 7.40-7.36 (m, 6H, H.sub.ar), 7.33-7.29 (m, 9H, H.sub.ar), 7.27 (dd, =7.2 Hz, J.sub.2=12.9 Hz, 1H, H.sub.ar), 7.20 (d, J=7.2 Hz, 1H, H.sub.ar), 7.14 (dd, =5.7 Hz, J.sub.2=8.5 Hz, 2H, H.sub.ar), 6.94 (t, J=8.8 Hz, 2H, H.sub.ar), 6.88 (dd, =8.1 Hz, J.sub.2=11.0 Hz, 1H, H.sub.ar), 5.57 (s, 1H, CH). .sup.13C NMR (125 MHz, CDCl.sub.3) 162.25 (d, J=244.6 Hz), 154.33 (d, J=21.6 Hz), 140.13, 136.54 (d, J=14.5 Hz), 132.28 (d, J=2.6 Hz), 131.49 (d, J=8.9 Hz), 29.46 (d, J=8.2 Hz), 128.14, 127.54, 127.44, 127.32, 124.83 (d, J=15.0 Hz), 115.17, 115.0, 76.19. .sup.31P NMR (203 MHz, CDCl.sub.3) 51.96 HRMS (ESI) calculated [M+H].sup.+ for C.sub.31H.sub.25FOP: 463.1622. found: 463.1649. FTIR (cm.sup.1) 3677, 3060, 2805, 1646, 1507, 1437, 1260, 1103, 827, 742.

Example 7: Synthesis of 1,1,1-Triphenyl-3-(4-(trifluoromethyl)phenyl)-1,3-dihydro-15-benzo[c][1,2] oxaphosphole (4g)

(90) ##STR00056##

(91) Following the general procedure, treatment of 2-(trimethylsilyl)phenyl trifluoromethanesulfonate 1a (0.179 g, 146 L, 0.6 mmol) and 4-(trifluoromethyl)benzaldehyde 1b (0.131 g, 102 L, 0.75 mmol) with triphenylphosphine 1c (0.131 g, 0.5 mmol) in the presence of KF (0.070 g, 1.2 mmol) and 18-crown-6 (0.317 g, 1.2 mmol) in THF (3.0 mL) at 10 C. to rt for 12 h followed by flash column chromatography (Pet. ether/EtOAc=40/60) of the crude reaction mixture using silica gel afforded 1,1,1-Triphenyl-3-(4-(trifluoromethyl)phenyl)-1,3-dihydro-1.sup.5-benzo[c][1,2]oxaphosphole 4g as a white solid (0.199 g, 78% yield).

(92) R.sub.f (EtOAc): 0.58; .sup.1H NMR (500 MHz, CDCl.sub.3) 7.47 (d, J=8.0 Hz, 3H, H.sub.ar), 7.38-7.28 (m, 15H, H.sub.ar), 7.24-7.19 (m, 4H, H.sub.ar), 6.89 (dd, =8.3 Hz, J.sub.2=11.2 Hz, 1H, H.sub.ar), 5.68 (s, 1H, CH). .sup.13C NMR (125 MHz, CDCl.sub.3) 153.37 (d, J=21.2 Hz), 148.43, 143.40, 142.55, 136.69 (d, J=14.3 Hz), 132.38 (d, J=2.9 Hz), 132.13 (d, J=9.8 Hz), 132.00 (d, J=2.4 Hz), 131.34 (d, J=8.8 Hz), 129.35 (q, J=31.83 Hz), 128.20, 127.91, 127.49 (d, J=13.4 Hz), 125.15 (d, J=3.5 Hz), 124.74 (d, J=15.2 Hz), 76.46. .sup.31P NMR (203 MHz, CDCl.sub.3) 50.16. HRMS (ESI) calculated [M+H].sup.+ for C.sub.32H.sub.25F.sub.3OP: 513.1590. found: 513.1602. FTIR (cm.sup.1) 3842, 3062, 2360, 1916, 1583, 1486, 1198, 1027, 739, 664.

Example 8: Synthesis of Methyl-4-(1,1,1-triphenyl-1,3-dihydro-15-benzo[c][1,2] oxaphosphol-3-yl) benzoate (4h)

(93) ##STR00057##

(94) Following the general procedure, treatment of 2-(trimethylsilyl)phenyl trifluoromethanesulfonate 1a (0.179 g, 146 L, 0.60 mmol) and methyl 4-formylbenzoate 1b (0.123 g, 0.75 mmol) with triphenylphosphine 1c (0.131 g, 0.50 mmol) in the presence of KF (0.070 g, 1.20 mmol) and 18-crown-6 (0.317 g, 120 mmol) in THF (3.0 mL) at 10 C. to rt for 12 h followed by flash column chromatography (Pet. ether/EtOAc=40/60) of the crude reaction mixture using silica gel afforded methyl-4-(1,1,1-triphenyl-1,3-dihydro-1.sup.5-benzo[c][1,2]oxaphosphol-3-yl)benzoate 4h as a white solid (0.227 g, 90% yield).

(95) R.sub.f (EtOAc): 0.47; .sup.1H NMR (500 MHz, CDCl.sub.3) 7.93 (d, J=6.9 Hz, 2H, H.sub.ar), 7.48 (t, J=6.5 Hz, 1H, H.sub.ar), 7.40-7.37 (m, 6H, H.sub.ar), 7.33-7.29 (m, 9H, H.sub.ar), 7.27-7.24 (m, 1H, H.sub.ar), 7.21 (d, J=7.2 Hz, 3H, H.sub.ar), 6.87 (t, J=9.2 Hz, 1H, H.sub.ar), 5.70 (s, 1H, CH), 3.90 (s, 3H, CH.sub.3). .sup.13C NMR (125 MHz, CDCl.sub.3) 167.19, 153.56 (d, J=21.5 Hz), 149.72, 143.72, 142.88, 136.71 (d, J=14.6 Hz), 132.39 (d, J=2.5 Hz), 131.43 (d, J=8.7 Hz), 129.68, 129.06, 128.83, 128.19, 127.70, 127.58, 127.48, 124.75 (d, J=15.2 Hz), 76.70, 52.09. .sup.31P NMR (203 MHz, CDCl.sub.3) 50.75 HRMS (ESI) calculated [M+H].sup.+ for C.sub.33H.sub.28O.sub.3P: 503.1771. found: 503.1788. FTIR (cm.sup.1) 3829, 3744, 3678, 3649, 3008, 2319, 1712, 1647, 1614. 1469. 1369. 1279, 1217, 1112, 1041, 986, 872, 834.

Example 9: Synthesis of 4-(1,1,1-Triphenyl-1,3-dihydro-15-benzo[c][1,2]oxaphosphol-3-yl)benzonitrile (4i)

(96) ##STR00058##

(97) Following the general procedure, treatment of 2-(trimethylsilyl)phenyl trifluoromethanesulfonate 1a (0.179 g, 146 L, 0.60 mmol) and 4-formylbenzonitrile 1b (0.098 g, 0.75 mmol) with triphenylphosphine 1c (0.131 g, 0.50 mmol) in the presence of KF (0.070 g, 1.20 mmol) and 18-crown-6 (0.317 g, 1.20 mmol) in THF (3.0 mL) at 10 C. to rt for 12 h followed by flash column chromatography (Pet. ether/EtOAc=40/60) of the crude reaction mixture using silica gel afforded 4-(1,1,1-triphenyl-1,3-dihydro-1.sup.5-benzo[c][1,2]oxaphosphol-3-yl)benzonitrile 4i as a white solid (0.206 g, 83% yield).

(98) R.sub.f (EtOAc): 0.51; .sup.1H NMR (400 MHz, CDCl.sub.3) 7.51 (d, J=6.7 Hz, 3H, H.sub.ar), 7.37-7.28 (m, 16H, H.sub.ar), 7.20 (d, J=7.2 Hz, 3H, H.sub.ar), 6.90 (t, J=8.5 Hz, 1H, H.sub.ar), 5.73 (s, 1H, CH). .sup.13C NMR (100 MHz, CDCl.sub.3) 152.84 (d, J=21.4 Hz), 150.03, 143.56, 142.54, 136.93 (d, J=14.6 Hz), 132.59, 132.15, 131.38 (d, J=8.4 Hz), 128.39, 128.29, 127.80, 127.64 (d, J=12.3 Hz), 124.75, 119.11, 110.95, 76.57. .sup.31P NMR (162 MHz, CDCl.sub.3) 50.08. HRMS (ESI) calculated [M+H].sup.+ for C.sub.32H.sub.25NOP: 470.1668. found: 470.1672. FTIR (cm.sup.1) 3829, 3677, 3005, 1735, 1645, 1595, 1487, 1399, 1373, 1249, 1111, 1062, 846, 744, 699.

Example 10: Synthesis of 3-(3-Methoxyphenyl)-1,1,1-triphenyl-1,3-dihydro-15-benzo [c][1,2] oxaphosphole (4j)

(99) ##STR00059##

(100) Following the general procedure, treatment of 2-(trimethylsilyl)phenyl trifluoromethanesulfonate 1a (0.179 g, 146 L, 0.6 mmol) and 3-methoxybenzaldehyde 1b (0.102 g, 91 L, 0.75 mmol) with triphenylphosphine 1c (0.131 g, 0.5 mmol) in the presence of KF (0.070 g, 1.20 mmol) and 18-crown-6 (0.317 g, 1.20 mmol) in THF (3.0 mL) at 10 C. to rt for 12 h followed by flash column chromatography (Pet. ether/EtOAc=40/60) of the crude reaction mixture using silica gel afforded 3-(3-methoxyphenyl)-1,1,1-triphenyl-1,3-dihydro-1.sup.5-benzo[c][1,2]oxaphosphole 4j as a white solid (0.192 g, 81% yield).

(101) R.sub.f (EtOAc): 0.50; .sup.1H NMR (500 MHz, CDCl.sub.3) 7.46 (t, J=7.2 Hz, 1H, H.sub.ar), 7.40-7.38 (m, 6H, H.sub.ar), 7.33-7.26 (m, 10H, H.sub.ar), 7.23-7.16 (m, 2H, H.sub.ar), 6.85-6.81 (m, 2H, H.sub.ar), 6.74 (d, J=8.0 Hz, 1H, H.sub.ar), 6.59 (s, 1H, H.sub.ar), 5.66 (s, 1H, CH), 3.58 (s, 3H, OCH.sub.3). .sup.13C NMR (125 MHz, CDCl.sub.3) 159.76, 154.33 (d, J=21.9 Hz), 146.01, 144.10, 143.26, 136.55 (d, J=14.5 Hz), 132.36, 131.43 (d, J=8.8 Hz), 129.10, 128.05, 127.50 (d, J=12.2 Hz), 127.27 (d, J=14.2 Hz), 124.86 (d, J=15.4 Hz), 120.12, 113.83, 112.05, 77.23, 55.20. .sup.31P NMR (203 MHz, CDCl.sub.3) 51.37 HRMS (ESI) calculated [M+H].sup.+ for C.sub.32H.sub.28O.sub.2P: 475.1821. found: 475.1852. FTIR (cm.sup.1) 3678, 3015, 2361, 1647, 1462, 1215, 1052, 741, 667.

Example 11: Synthesis of 3-(3-Bromophenyl)-1,1,1-triphenyl-1,3-dihydro-15-benzo[c][1,2] oxaphosphole (4k)

(102) ##STR00060##

(103) Following the general procedure, treatment of 2-(trimethylsilyl)phenyl trifluoromethanesulfonate 1a (0.179 g, 146 L, 0.60 mmol) and 3-bromobenzaldehyde 1b (0.139 g, 88 L, 0.75 mmol) with triphenylphosphine 1c (0.131 g, 0.50 mmol) in the presence of KF (0.070 g, 1.20 mmol) and 18-crown-6 (0.317 g, 1.20 mmol) in THF (3.0 mL) at 10 C. to rt for 12 h followed by flash column chromatography (Pet. ether/EtOAc=40/60) of the crude reaction mixture using silica gel afforded 3-(3-bromophenyl)-1,1,1-triphenyl-1,3-dihydro-1.sup.5-benzo[c][1,2]oxaphosphole 4k as a white solid (0.194 g, 74% yield).

(104) R.sub.f (EtOAc): 0.52; .sup.1H NMR (400 MHz, CDCl.sub.3) 7.48 (t, J=6.8 Hz, 1H, H.sub.ar), 7.41-7.38 (m, 4H, H.sub.ar), 7.36 (bs, 2H, H.sub.ar), 7.33-7.29 (m, 10H, H.sub.ar), 7.26-7.21 (m, 2H, H.sub.ar), 7.16-7.08 (m, 3H, H.sub.ar), 6.88 (dd, J.sub.1=8.0 Hz, J.sub.2=11.3 Hz, 1H, H.sub.ar), 5.65 (s, 1H, CH). .sup.13C NMR (100 MHz, CDCl.sub.3) 153.53 (d, J=21.1 Hz), 146.78, 143.35, 142.32, 136.69 (d, J=14.5 Hz), 132.46 (d, J=2.9 Hz), 131.44 (d, J=8.9 Hz), 130.75, 130.28, 129.74, 128.31 (d, J=1.8 Hz), 127.61, 127.49, 126.22, 124.96 (d, J=15.2 Hz), 122.51, 76.45. .sup.31P NMR (162 MHz, CDCl.sub.3) 49.87 HRMS (ESI) calculated [M+H].sup.+ for C.sub.31H.sub.25BrOP: 523.0821. found: 523.0826. FTIR (cm.sup.1) 3894, 3860, 3743, 3678, 3619, 3012, 2362, 1836, 1741, 1693, 1647, 1516, 1479, 1429, 1217, 1184, 1065, 910, 742.

Example 12: Synthesis of 3-(3-Nitrophenyl)-1,1,1-triphenyl-1,3-dihydro-15-benzo [c][1,2]oxaphosphole (4l)

(105) ##STR00061##

(106) Following the general procedure, treatment of 2-(trimethylsilyl)phenyl trifluoromethanesulfonate 1a (0.179 g, 146 L, 0.6 mmol) and 3-nitrobenzaldehyde 1b (0.113 g, 0.75 mmol) with triphenylphosphine 1c (0.131 g, 0.5 mmol) in the presence of KF (0.070 g, 1.2 mmol) and 18-crown-6 (0.317 g, 1.20 mmol) in THF (3.0 mL) at 10 C. to rt for 12 h followed by flash column chromatography (Pet. ether/EtOAc=40/60) of the crude reaction mixture using silica gel afforded 3-(3-nitrophenyl)-1,1,1-triphenyl-1,3-dihydro-1.sup.5-benzo[c] [1,2]oxaphosphole 4l as a white solid (0.186 g, 76% yield).

(107) R.sub.f (EtOAc): 0.47; .sup.1H NMR (500 MHz, CDCl.sub.3) 8.06 (d, J=8.0 Hz, 1H, H.sub.ar), 7.96 (s, 1H, H.sub.ar), 7.53-7.49 (m, 2H, H.sub.ar), 7.40-7.34 (m, 16H, H.sub.ar), 7.29-7.27 (m, 1H, H.sub.ar), 7.24 (d, J=7.0 Hz, 1H, H.sub.ar), 6.93 (dd, =8.2 Hz, J.sub.2=11.3 Hz, 1H, H.sub.ar), 5.81 (s, 1H, CH). .sup.13C NMR (125 MHz, CDCl.sub.3) 153.95 (d, J=20.6 Hz), 148.38, 146.98, 137.0 (d, J=14.77 Hz), 133.76, 132.65 (d, J=2.6 Hz), 131.30 (d, J=8.8 Hz), 129.12, 128.42, 127.85, 127.74, 127.64, 124.79 (d, J=15.2 Hz), 122.70, 122.32, 76.40. .sup.31P NMR (203 MHz, CDCl.sub.3) 49.49. HRMS (ESI) calculated [M+H].sup.+ for C.sub.31H.sub.25NO.sub.3P: 490.1567. found: 490.1584. FTIR (cm.sup.1) 3743, 3060, 2361, 1580, 1529, 1349, 1064, 999, 693.

Example 13: Synthesis of 1,1,1-Triphenyl-3-(o-tolyl)-1,3-dihydro-15-benzo[c][1,2]oxaphosphole (4m)

(108) ##STR00062##

(109) Following the general procedure, treatment of 2-(trimethylsilyl)phenyl trifluoromethanesulfonate 1a (0.179 g, 146 L, 0.6 mmol) and 2-methylbenzaldehyde 1b (0.090 g, 87 L, 0.75 mmol) with triphenylphosphine 1c (0.131 g, 0.5 mmol) in the presence of KF (0.070 g, 1.2 mmol) and 18-crown-6 (0.317 g, 1.2 mmol) in THF (3.0 mL) at 10 C. to rt for 12 h followed by flash column chromatography (Pet. ether/EtOAc=40/60) of the crude reaction mixture using silica gel afforded 1,1,1-triphenyl-3-(o-tolyl)-1,3-dihydro-1.sup.5-benzo[c][1,2]oxaphosphole 4m as a white solid (0.147 g, 64% yield).

(110) R.sub.f (EtOAc): 0.42; .sup.1H NMR (500 MHz, CDCl.sub.3) 7.45-7.37 (m, 7H, H.sub.ar), 7.30-7.26 (m, 9H, H.sub.ar), 7.24-7.20 (m, 1H, H.sub.ar), 7.12-7.09 (m, 3H, H.sub.ar), 7.06-7.03 (m, 1H, H.sub.ar), 6.96 (d, J=7.36 Hz, 1H, H.sub.ar), 6.89 (dd, (dd, J.sub.1=8.3 Hz, J.sub.2=10.8 Hz, 1H, H.sub.ar), 5.32 (s, 1H, CH), 2.31 (s, 3H, CH.sub.3). .sup.13C NMR (125 MHz, CDCl.sub.3) 154.74 (d, J=20.1 Hz), 141.98, 136.49 (d, J=14.3 Hz), 136.0, 132.18 (d, J=2.6 Hz), 131.64 (d, J=9.1 Hz), 130.28, 128.30, 128.14, 127.47 (d, J=12.3 Hz), 127.21, 127.14, 127.10, 126.23, 124.77 (d, J=15.0 Hz), 72.40, 19.74. .sup.31P NMR (203 MHz, CDCl.sub.3) 52.37. HRMS (ESI) calculated [M+H].sup.+ for C.sub.32H.sub.28OP: 459.1872. found: 459.1873. FTIR (cm.sup.1) 3828, 3060, 2361, 1835, 1741, 1484, 1264, 1050, 742, 665.

Example 14: Synthesis of 3-(2-Fluorophenyl)-1,1,1-triphenyl-1,3-dihydro-15-benzo[c][1,2]oxaphosphole (4n)

(111) ##STR00063##

(112) Following the general procedure, treatment of 2-(trimethylsilyl)phenyl trifluoromethanesulfonate 1a (0.179 g, 146 L, 0.60 mmol) and 2-fluorobenzaldehyde 1b (0.093 g, 80 L, 0.75 mmol) with triphenylphosphine 1c (0.131 g, 0.50 mmol) in the presence of KF (0.070 g, 1.20 mmol) and 18-crown-6 (0.317 g, 1.20 mmol) in THF (3.0 mL) at 10 C. to rt for 12 h followed by flash column chromatography (Pet. ether/EtOAc=40/60) of the crude reaction mixture using silica gel afforded 3-(2-fluorophenyl)-1,1,1-triphenyl-1,3-dihydro-1.sup.5-benzo[c][1,2]oxaphosphole 4n as a white solid (0.199 g, 86% yield).

(113) R.sub.f (EtOAc): 0.49; .sup.1H NMR (400 MHz, CDCl.sub.3) 7.49 (t, J=6.9 Hz, 1H, H.sub.ar), 7.42-7.36 (m, 7H, H.sub.ar), 7.33-7.29 (m, 9H, H.sub.ar), 7.25-7.20 (m, 1H, H.sub.ar), 7.18-7.13 (m, 1H, H.sub.ar), 7.03 (t, J=9.7 Hz, 1H, H.sub.ar), 6.91-6.60 (m, 3H, H.sub.ar), 6.06 (s, 1H, CH). .sup.13C NMR (100 MHz, CDCl.sub.3) 160.65 (d, J.sub.C-F=245.3 Hz), 153.91 (d, J=20.1 Hz), 143.60, 142.53, 136.66 (d, J=14.6 Hz), 132.60 (d, J=2.8 Hz), 131.73, 131.60, 131.44 (d, J=8.9 Hz), 129.42 (d, J=4.2 Hz), 128.67 (d, J=8.2 Hz), 128.23 (d, J=1.2 Hz), 127.61, 127.49, 127.30, 124.78 (dd, J.sub.1=2.6 Hz, J.sub.2=15.2 Hz), 124.23 (d, J=3.0 Hz), 115.10, 70.72. .sup.31P NMR (162 MHz, CDCl.sub.3) 51.40 HRMS (ESI) calculated [M+H].sup.+ for C.sub.31H.sub.25FOP: 463.1622. found: 463.1646. FTIR (cm.sup.1) 3925, 3861, 3143, 3648, 3061, 3004, 2362, 1835, 1707, 1648, 1547, 1395, 1263, 1222, 1107, 1062, 808, 745, 667.

Example 15: Synthesis of 3-(3,4-Dichlorophenyl)-1,1,1-triphenyl-1,3-dihydro-15-benzo[c][1,2]oxaphosphole (4o)

(114) ##STR00064##

(115) Following the general procedure, treatment of 2-(trimethylsilyl)phenyl trifluoromethanesulfonate 1a (0.179 g, 146 L, 0.60 mmol) and 3,4-dichlorobenzaldehyde 1b (0.131 g, 0.75 mmol) with triphenylphosphine 1c (0.131 g, 0.50 mmol) in the presence of KF (0.070 g, 1.20 mmol) and 18-crown-6 (0.317 g, 1.20 mmol) in THF (3.0 mL) at 10 C. to rt for 12 h followed by flash column chromatography (Pet. ether/EtOAc=40/60) of the crude reaction mixture using silica gel afforded 3-(3,4-dichlorophenyl)-1,1,1-triphenyl-1,3-dihydro-1.sup.5-benzo[c][1,2]oxaphosphole 4o as a white solid (0.210 g, 82% yield).

(116) R.sub.f (EtOAc): 0.48; .sup.1H NMR (400 MHz, CDCl.sub.3) 7.52-7.48 (m, 1H, H.sub.ar), 7.37-7.29 (m, 15H, H.sub.ar), 7.28-7.22 (m, 3H, H.sub.ar), 7.07 (bs, 1H, H.sub.ar), 6.98 (dd, =1.9 Hz, J.sub.2=8.3 Hz, 1H, H.sub.ar), 6.87 (dd, =8.0 Hz, J.sub.2=11.7 Hz, 1H, H.sub.ar), 5.64 (s, 1H, CH). .sup.13C NMR (100 MHz, CDCl.sub.3) 153.18 (d, J=20.6 Hz), 144.96, 142.31, 136.85 (d, J=14.5 Hz), 132.60, 132.29, 131.43 (d, J=8.8 Hz), 131.02, 130.13, 129.68, 128.42, 127.64, (d, J=12.3 Hz), 126.88, 124.91 (d, J=14.5 Hz), 76.08. .sup.31P NMR (162 MHz, CDCl.sub.3) 49.64 HRMS (ESI) calculated [M+H].sup.+ for C.sub.31H.sub.24Cl.sub.2OP: 513.0936. found: 513.0968. FTIR (cm.sup.1) 3925, 3861, 2829, 3677, 3619. 3059, 2978, 2361, 1835, 1707, 1693, 1547, 1482, 1395, 1258, 1118, 894, 745, 716.

Example 16: Synthesis of 3-Mesityl-1,1,1-triphenyl-1,3-dihydro-15-benzo[c][1,2] oxaphosphole (4p)

(117) ##STR00065##

(118) Following the general procedure, treatment of 2-(trimethylsilyl)phenyl trifluoromethanesulfonate 1a (0.179 g, 146 L, 0.60 mmol) and 2,4,6-trimethylbenzaldehyde 1b (0.111 g, 111 L, 0.75 mmol) with triphenylphosphine 1c (0.131 g, 0.50 mmol) in the presence of KF (0.070 g, 1.20 mmol) and 18-crown-6 (0.317 g, 1.20 mmol) in THF (3.0 mL) at 10 C. to rt for 12 h followed by flash column chromatography (Pet. ether/EtOAc=40/60) of the crude reaction mixture using silica gel afforded 3-mesityl-1,1,1-triphenyl-1,3-dihydro-1.sup.5-benzo[c][1,2]oxaphosphole 4p as a white solid (0.151 g, 62% yield).

(119) R.sub.f (EtOAc): 0.29; .sup.1H NMR (400 MHz, CDCl.sub.3) 7.49-7.41 (m, 7H, H.sub.ar), 7.32 (bs, 9H, H.sub.ar), 7.27-7.17 (m, 1H, H.sub.ar), 7.07-7.03 (m, 2H, H.sub.ar), 6.76 (bs, 2H, H.sub.ar), 5.62 (s, 1H, CH), 2.23 (s, 3H, CH.sub.3), 2.09 (s, 3H, CH.sub.3), 1.86 (s, 3H, CH.sub.3). .sup.13C NMR (100 MHz, CDCl.sub.3) 155.41 (d, J=19.4 Hz), 141.84, 140.79, 138.04, 137.38, 136.90, 136.49 (d, J=13.8 Hz), 134.05, 132.10, 131.71 (d, J=8.7 Hz), 130.76, 128.87, 128.33, 127.52 (d, J=12.3 Hz), 126.81 (d, J=14.3 Hz), 123.47 (d, J=14.6 Hz), 70.45, 21.13, 20.96, 20.53. .sup.31P NMR (162 MHz, CDCl.sub.3) 49.31 HRMS (ESI) calculated [M+H].sup.+ for C.sub.34H.sub.32OP: 487.2185. found: 487.2185. FTIR (cm.sup.1) 3759, 3672, 3063, 3013, 2926, 2855, 1891, 1626, 1517, 1438, 1342, 1273, 1071, 987, 839, 744.

Example 17: Synthesis of 3-(Naphthalen-2-yl)-1,1,1-triphenyl-1,3-dihydro-15-benzo [c][1,2]oxaphosphole (4q)

(120) ##STR00066##

(121) Following the general procedure, treatment of 2-(trimethylsilyl)phenyl trifluoromethanesulfonate 1a (0.179 g, 146 L, 0.60 mmol) and 2-naphthaldehyde 1b (0.117 g, 0.75 mmol) with triphenylphosphine 1c (0.131 g, 0.50 mmol) in the presence of KF (0.070 g, 1.20 mmol) and 18-crown-6 (0.317 g, 1.20 mmol) in THF (3.0 mL) at 10 C. to rt for 12 h followed by flash column chromatography (Pet. ether/EtOAc=40/60) of the crude reaction mixture using silica gel afforded 3-(naphthalen-2-yl)-1,1,1-triphenyl-1,3-dihydro-1.sup.5-benzo[c][1,2] oxaphosphole 4q as a white solid (0.195 g, 79% yield).

(122) R.sub.f (EtOAc): 0.54; .sup.1H NMR (500 MHz, CDCl.sub.3) 7.65-7.64 (m, 1H, H.sub.ar), 7.60 (d, J=8.5 Hz, 1H, H.sub.ar), 7.54-7.53 (m, 1H, H.sub.ar), 7.43 (s, 1H, H.sub.ar), 7.36-7.28 (m, 9H, H.sub.ar), 7.20 (bs, 9H, H.sub.ar), 7.15-7.07 (m, 3H, H.sub.ar), 6.74 (d, J=10.3 Hz, 2H, H.sub.ar), 5.68 (s, 1H, CH). .sup.13C NMR (125 MHz, CDCl.sub.3) 154.31 (d, J=21.9 Hz), 143.96, 143.10, 141.63, 136.57 (d, J=14.5 Hz), 133.37, 132.99, 132.30 (d, J=2.1 Hz), 132.24, 131.59 (d, J=8.9 Hz), 128.63 (d, J=12.1 Hz), 128.12, 128.03 (d, J=6.8 Hz), 127.66, 127.50 (d, J=12.3 Hz), 127.28, 126.92, 125.81 (d, J=8.9 Hz), 125.60, 125.02 (d, J=15.5 Hz), 77.16 (merged with the CDCl.sub.3 peak). .sup.31P NMR (203 MHz, CDCl.sub.3) 49.43 HRMS (ESI) calculated [M+H].sup.+ for C.sub.35H.sub.28OP: 495.1872. found: 495.1876. FTIR (cm.sup.1) 3843, 3648, 3590, 3063, 2926, 2321, 1635, 1607, 1514, 1432, 1292, 1185, 1083, 889, 815, 751, 696.

Example 18: Synthesis of 1,1,1-Triphenyl-3-(pyren-4-yl)-1,3-dihydro-15-benzo[c][1,2]oxaphosphole (4r)

(123) ##STR00067##

(124) Following the general procedure, treatment of 2-(trimethylsilyl)phenyl trifluoromethanesulfonate 1a (0.179 g, 146 L, 0.60 mmol) and pyrene-4-carbaldehyde 1b (0.173 g, 0.75 mmol) with triphenylphosphine 1c (0.131 g, 0.50 mmol) in the presence of KF (0.070 g, 1.20 mmol) and 18-crown-6 (0.317 g, 1.20 mmol) in THF (3.0 mL) at 10 C. to rt for 12 h followed by flash column chromatography (Pet. ether/EtOAc=40/60) of the crude reaction mixture using silica gel afforded 1,1,1-triphenyl-3-(pyren-4-yl)-1,3-dihydro-1.sup.5-benzo[c][1,2]oxaphosphole 4r as a yellow solid (0.201 g, 71% yield).

(125) R.sub.f (EtOAc): 0.53; .sup.1H NMR (400 MHz, CDCl.sub.3) 8.46 (d, J=9.4 Hz, 1H, H.sub.ar), 8.19 (d, J=7.6 Hz, 2H, H.sub.ar), 8.11 (d, J=9.4 Hz, 1H, H.sub.ar), 8.07-8.04 (m, 3H, H.sub.ar), 8.00 (d, J 7.7 Hz, 1H, H.sub.ar), 7.75 (d, J=8.0 Hz, 1H, H.sub.ar), 7.60-7.50 (m, 6H, H.sub.ar), 7.40-7.34 (m, 10H, H.sub.ar), 7.29-7.22 (m, 2H, H.sub.ar), 7.04 (dd, =8.3 Hz, J.sub.2=11.2 Hz, 1H, H.sub.ar), 6.77 (s, 1H, CH). .sup.13C NMR (100 MHz, CDCl.sub.3) 154.84 (d, J=21.0 Hz), 143.60, 142.55, 137.94, 136.72 (d, J=14.4 Hz), 132.33 (d, J=2.7 Hz), 132.22, 132.12, 131.62 (d, J=8.9 Hz), 131.46, 130.80, 130.57, 129.46, 128.93, 128.66, 128.54, 128.25, 127.56 (d, J=12.6 Hz), 127.44, 127.04, 125.96, 125.82, 125.23 (d, J=15.9 Hz), 124.92 (d, J=16.8 Hz), 123.60, 73.01. .sup.31P NMR (162 MHz, CDCl.sub.3) 50.44 HRMS (ESI) calculated [M+H].sup.+ for C.sub.41H.sub.30OP: 569.2029. found: 569.2029. FTIR (cm.sup.1) 2985, 1733, 1438, 1372, 1241, 1194, 1045, 939, 847, 754, 696, 654, 639.

Example 19: Synthesis of 3-(Benzofuran-2-yl)-1,1,1-triphenyl-1,3-dihydro-15-benzo [c] [1,2] oxaphosphole (4s)

(126) ##STR00068##

(127) Following the general procedure, treatment of 2-(trimethylsilyl)phenyl trifluoromethanesulfonate 1a (0.179 g, 146 L, 0.60 mmol) and benzofuran-2-carbaldehyde 1b (0.110 g, 91 L, 0.75 mmol) with triphenylphosphine 1c (0.131 g, 0.50 mmol) in the presence of KF (0.070 g, 1.20 mmol) and 18-crown-6 (0.317 g, 1.20 mmol) in THF (3.0 mL) at 10 C. to rt for 12 h followed by flash column chromatography (Pet. ether/EtOAc=40/60) of the crude reaction mixture using silica gel afforded 3-(benzofuran-2-yl)-1,1,1-triphenyl-1,3-dihydro-1.sup.5-benzo[c][1,2] oxaphosphole 4s as a white solid (0.203 g, 83% yield).

(128) R.sub.f (EtOAc): 0.36; .sup.1H NMR (400 MHz, CDCl.sub.3) 7.65-7.63 (m, 1H, H.sub.ar), 7.60-7.56 (m, 1H, H.sub.ar), 7.52-7.43 (m, 8H, H.sub.ar), 7.39-7.31 (m, 9H, H.sub.ar), 7.29-7.25 (m, 2H, H.sub.ar), 7.23-7.20 (m, 1H, H.sub.ar), 6.83 (dd, J.sub.1=8.0 Hz, J.sub.2=11.3 Hz, 1H), 6.35 (s, 1H), 5.92 (s, 1H). .sup.13C NMR (100 MHz, CDCl.sub.3) 159.23, 155.21, 150.81 (d, J=20.4 Hz), 143.66, 142.60, 136.88 (d, J=14.3 Hz), 132.52 (d, J=3.0 Hz), 131.69 (d, J=9.0 Hz), 128.43, 128.26 (d, J=2.2 Hz), 127.99 (d, J=14.2 Hz), 127.46 (d, J=12.5 Hz), 124.82 (d, J=15.1 Hz), 123.70, 122.47, 120.92, 111.91, 103.94, 70.49. .sup.31P NMR (162 MHz, CDCl.sub.3) 43.56 HRMS (ESI) calculated [M+H].sup.+ for C.sub.33H.sub.26OP: 485.1665. found: 485.1674. FTIR (cm.sup.1) 3893, 3843, 3743, 3678, 3648, 3619, 3015, 2396, 1741, 1693, 1647, 1516, 1461, 1216, 1117, 741, 668.

Example 20: Synthesis of 1,1,1-Triphenyl-3-(thiophen-2-yl)-1,3-dihydro-15-benzo [c][1,2] oxaphosphole (4t)

(129) ##STR00069##

(130) Following the general procedure, treatment of 2-(trimethylsilyl)phenyl trifluoromethanesulfonate 1a (0.179 g, 146 L, 0.60 mmol) and thiophene-2-carbaldehyde 1b (0.084 g, 70 L, 0.75 mmol) with triphenylphosphine 1c (0.131 g, 0.50 mmol) in the presence of KF (0.070 g, 1.2 mmol) and 18-crown-6 (0.317 g, 1.2 mmol) in THF (3.0 mL) at 10 C. to rt for 12 h followed by flash column chromatography (Pet. ether/EtOAc=40/60) of the crude reaction mixture using silica gel afforded 1,1,1-triphenyl-3-(thiophen-2-yl)-1,3-dihydro-1.sup.5-benzo[c][1,2]oxaphosphole 4t as a white solid (0.149 g, 66% yield).

(131) R.sub.f (EtOAc): 0.39 .sup.1H NMR (500 MHz, CDCl.sub.3) 7.52 (t, J=6.2 Hz, 1H, H.sub.ar), 7.44-7.41 (m, 6H, H.sub.ar), 7.39-7.34 (m, 10H, H.sub.ar), 7.27-7.23 (m, 1H, H.sub.ar), 7.20 (d, J=4.7 Hz, 1H, H.sub.ar), 7.02 (s, 1H, H.sub.ar), 6.94 (bs, 1H), 6.84 (t, J=8.6 Hz, 1H, H.sub.ar), 5.83 (s, 1H, CH). .sup.13C NMR (125 MHz, CDCl.sub.3) 153.78 (d, J=20.6 Hz), 148.64, 143.40, 142.55, 136.36 (d, J=14.4 Hz), 132.30 (d, J=2.8 Hz), 131.56 (d, J=9.1 Hz), 128.11, 127.66, 127.54, 127.38 (d, J=12.1 Hz), 126.09, 125.16 (d, J=11.9 Hz), 124.75 (d, J=15.7 Hz), 71.95. .sup.31P NMR (203 MHz, CDCl.sub.3) 51.66 HRMS (ESI) calculated [M+H].sup.+ for C.sub.29H.sub.24OPS: 451.1280. found: 451.1279. FTIR (cm.sup.1) 3894, 3861, 3678, 3648, 3619, 3011, 2873, 2362, 1836, 1741, 1693, 1647, 1464, 1216, 1116. 1030. 948, 741, 656.

Example 21: Synthesis of 3-Cyclohexyl-1,1,1-triphenyl-1,3-dihydro-15-benzo[c][1,2]oxaphosphole (4u)

(132) ##STR00070##

(133) Following the general procedure, treatment of 2-(trimethylsilyl)phenyl trifluoromethanesulfonate 1a (0.179 g, 146 L, 0.60 mmol) and cyclohexanecarbaldehyde 1b (0.084 g, 91 L, 0.75 mmol) with triphenylphosphine 1c (0.131 g, 0.50 mmol) in the presence of KF (0.070 g, 1.20 mmol) and 18-crown-6 (0.317 g, 1.20 mmol) in THF (3.0 mL) at 10 C. to rt for 12 h followed by flash column chromatography (Pet. ether/EtOAc=40/60) of the crude reaction mixture using silica gel afforded 3-cyclohexyl-1,1,1-triphenyl-1,3-dihydro-1.sup.5-benzo[c][1,2]oxaphosphole 4u as a white solid (0.191 g, 85% yield).

(134) R.sub.f (EtOAc): 0.33; .sup.1H NMR (500 MHz, CDCl.sub.3) 7.55 (s, 2H, H.sub.ar), 7.38-7.36 (m, 6H, H.sub.ar), 7.30-7.26 (m, 9H, H.sub.ar), 7.24 (bs, 1H, H.sub.ar), 6.91-6.89 (m, 1H, H.sub.ar), 4.64 (s, 1H, CH), 1.75 (bs, 2H), 1.63 (bs, 3H), 1.38-1.25 (m, 3H), 1.10-1.06 (m, 2H), 0.84-0.83 (m, 1H). .sup.13C NMR (125 MHz, CDCl.sub.3) 154.05 (d, J=24.2 Hz), 144.80, 143.96, 136.61 (d, J=14.5 Hz), 131.59 (d, J=8.8 Hz), 129.95, 127.64, 127.10 (d, J=12.1 Hz), 126.77 (d, J=14.1 Hz), 123.38 (d, J=15.7 Hz), 77.84, 44.07, 30.69, 27.18, 26.87, 26.65, 26.54. .sup.31P NMR (203 MHz, CDCl.sub.3) 52.53 HRMS (ESI) calculated [M+H].sup.+ for C.sub.31H.sub.32OP: 451.2185. found: 451.2185. FTIR (cm.sup.1) 3840, 3861, 3743, 3678, 3619, 3059, 3007. 2929, 2854, 2361, 1693, 1647, 1515, 1482, 1437, 1261, 1218, 1107, 1023, 860, 812, 743, 698.

Example 22: Synthesis of 3-Nonyl-1,1,1-triphenyl-1,3-dihydro-15-benzo[c][1,2] oxaphosphole (4v)

(135) ##STR00071##

(136) Following the general procedure, treatment of 2-(trimethylsilyl)phenyl trifluoromethanesulfonate 1a (0.179 g, 146 L, 0.60 mmol) and decanal 1b (0.117 g, 141 L, 0.75 mmol) with triphenylphosphine 1c (0.131 g, 0.50 mmol) in the presence of KF (0.070 g, 1.20 mmol) and 18-crown-6 (0.317 g, 1.20 mmol) in THF (3.0 mL) at 10 C. to rt for 12 h followed by flash column chromatography (Pet. ether/EtOAc=40/60) of the crude reaction mixture using silica gel afforded 3-nonyl-1,1,1-triphenyl-1,3-dihydro-1.sup.5-benzo[c][1,2]oxaphosphole 4v as a white solid (0.146 g, 59% yield).

(137) R.sub.f (EtOAc): 0.38; .sup.1H NMR (400 MHz, CDCl.sub.3) 7.57-7.53 (m, 1H, H.sub.ar), 7.51-7.49 (m, 1H, H.sub.ar), 7.35-7.33 (m, 4H, H.sub.ar), 7.31-7.25 (m, 11H, H.sub.ar), 7.22-7.18 (m, 1H, H.sub.ar), 6.74 (dd, J.sub.1=8.2 Hz, J.sub.2=11.3 Hz, 1H, H.sub.ar), 4.78 (dd, J.sub.1=4.1 Hz, J.sub.2=6.0 Hz, 1H, CH), 1.77-1.72 (m, 1H), 1.61-1.56 (m, 1H), 1.39-1.28 (m, 4H), 1.23 (bs, 4H), 1.14 (bs, 6H), 0.90 (t, J=6.8 Hz, 3H, CH.sub.3). NMR (100 MHz, CDCl.sub.3) 155.06 (d, J=22.8 Hz), 143.32, 142.27, 136.62 (d, J=14.5 Hz), 132.26 (d, J=2.7 Hz), 131.81 (d, J=8.9 Hz), 128.27, 127.42 (d, J=12.3 Hz), 126.98 (d, J=14.1 Hz), 123.76 (d, J=15.4 Hz), 73.18 (d, J=2.4 Hz), 37.13, 32.01, 29.91, 29.61, 29.56, 29.40, 25.21, 22.79, 14.24. .sup.31P NMR (162 MHz, CDCl.sub.3) 46.43 HRMS (ESI) calculated [M+H].sup.+ for C.sub.34H.sub.40OP: 495.2811. found: 495.2810. FTIR (cm.sup.1) 3842, 3743, 3616, 1063, 2927. 2855. 2360, 1742, 16932, 1648. 1488, 1436, 1293, 1180, 1117, 1081, 1003, 836, 744, 697.

Example 23: Synthesis of 1,1,1-Triphenyl-3-vinyl-1,3-dihydro-15-benzo[c][1,2] oxaphosphole (4w)

(138) ##STR00072##

(139) Following the general procedure, treatment of 2-(trimethylsilyl)phenyl trifluoromethanesulfonate 1a (0.179 g, 146 L, 0.60 mmol) and acrylaldehyde 1b (0.042 g, 50 L, 0.75 mmol) with triphenylphosphine 1c (0.131 g, 0.50 mmol) in the presence of KF (0.070 g, 1.20 mmol) and 18-crown-6 (0.317 g, 1.20 mmol) in THF (3.0 mL) at 10 C. to rt for 24 h followed by flash column chromatography (Pet. ether/EtOAc=40/60) of the crude reaction mixture using silica gel afforded 1, 1,1-triphenyl-3-vinyl-1,3-dihydro-1.sup.5-benzo[c][1,2]oxaphosphole 4w as a yellow solid (0.132 g, 67% yield).

(140) R.sub.f (EtOAc): 0.21; .sup.1H NMR (400 MHz, CDCl.sub.3) 7.60-7.56 (m, 1H, H.sub.ar), 7.50 (d, J=7.2 Hz, 1H, H.sub.ar), 7.38-7.36 (m, 4H, H.sub.ar), 7.34-7.27 (m, 11H, H.sub.ar), 7.25-7.22 (m, 1H, H.sub.ar), 6.73 (dd, J.sub.1=8.1 Hz, J.sub.2=10.9 Hz, 1H, H.sub.ar), 5.92-5.83 (m, 1H), 5.24 (d, J=17.0 Hz, 1H), 5.16-5.14 (m, 2H). .sup.13C NMR (100 MHz, CDCl.sub.3) 152.81 (d, J=22.7 Hz), 144.33, 143.28, 139.60, 136.68 (d, J=14.5 Hz), 132.20 (d, J=3.1 Hz), 131.52 (d, J=9.0 Hz), 127.99 (d, J=2.1 Hz), 127.36, 127.24, 124.34 (d, J=15.5 Hz), 116.10, 75.95. .sup.31P NMR (162 MHz, CDCl.sub.3) 51.78 HRMS (ESI) calculated [M+H].sup.+ for C.sub.27H.sub.24OP: 395.1559. found: 395.1559. FTIR (cm.sup.1) 3925, 3861, 3743, 3619, 3060, 2980, 2320, 1964, 1693, 1612, 1469, 1435, 1369, 1251, 1182, 1039, 938, 803, 692.

Example 24: Synthesis of 1,1,1-Triphenyl-3-styryl-1,3-dihydro-15-benzo[c][1,2] oxaphosphole (4x)

(141) ##STR00073##

(142) Following the general procedure, treatment of 2-(trimethylsilyl)phenyl trifluoromethanesulfonate 1a (0.179 g, 146 L, 0.60 mmol) and trans cinnamaldehyde 1b (0.099 g, 94 L, 0.75 mmol) with triphenylphosphine 1c (0.131 g, 0.50 mmol) in the presence of KF (0.070 g, 1.20 mmol) and 18-crown-6 (0.317 g, 1.20 mmol) in THF (3.0 mL) at 10 C. to rt for 24 h followed by flash column chromatography (Pet. ether/EtOAc=40/60) of the crude reaction mixture using silica gel afforded 1,1,1-triphenyl-3-styryl-1,3-dihydro-1.sup.5-benzo[c][1,2]oxaphosphole 4x as a yellow solid (0.156 g, 66% yield).

(143) R.sub.f (EtOAc): 0.30; .sup.1H NMR (400 MHz, CDCl.sub.3) 7.60-7.53 (m, 2H, H.sub.ar), 7.40-7.37 (m, 4H, H.sub.ar), 7.53-7.29 (m, 15H, H.sub.ar), 7.27-7.24 (m, 2H, H.sub.ar), 6.75 (dd, =8.2 Hz, J.sub.2=10.8 Hz, 1H), 6.49 (d, J=15.6 Hz, 1H), 6.23 (dd, J.sub.1=7.0 Hz, J.sub.2=15.7 Hz, 1H), 5.35 (s, 1H, CH). .sup.13C NMR (100 MHz, CDCl.sub.3) 153.17 (d, J=22.4 Hz), 144.59, 143.53, 137.23, 136.84 (d, J=14.6 Hz), 132.28 (d, J=2.9 Hz), 131.59 (d, J=8.9 Hz), 131.18 (d, J=9.9 Hz), 129.00, 128.45, 128.03, (d, J=2.0 Hz), 127.66, 127.58, 127.39 (d, J=12.3 Hz), 126.62, 124.45 (d, J=15.4 Hz), 75.35. .sup.31P NMR (162 MHz, CDCl.sub.3) 51.56 HRMS (ESI) calculated [M+H].sup.+ for C.sub.33H.sub.28OP: 471.1872. found: 471.1896. FTIR (cm.sup.1) 3829. 3743, 3678, 3648. 3061. 2980, 2320. 1738, 1647, 1609, 1469. 1433, 1370, 1250, 1195, 1112, 1039, 986, 872, 801, 742.

Example 25: Synthesis of 3-(4-Methoxystyryl)-1,1,1-triphenyl-1,3-dihydro-15-benzo[c][1,2] oxaphosphole (4y)

(144) ##STR00074##

(145) Following the general procedure, treatment of 2-(trimethylsilyl)phenyl trifluoromethanesulfonate 1a (0.179 g, 146 L, 0.60 mmol) and (E)-3-(4-methoxyphenyl)acrylaldehyde 1b (0.122 g, 0.75 mmol) with triphenylphosphine 1c (0.131 g, 0.50 mmol) in the presence of KF (0.070 g, 1.20 mmol) and 18-crown-6 (0.317 g, 1.20 mmol) in THF (3.0 mL) at 10 C. to rt for 24 h followed by flash column chromatography (Pet. ether/EtOAc=40/60) of the crude reaction mixture using silica gel afforded 3-(4-methoxystyryl)-1,1,1-triphenyl-1,3-dihydro-1.sup.5-benzo[c][1,2] oxaphosphole 4y as a yellow solid (0.153 g, 61% yield).

(146) R.sub.f (EtOAc): 0.27; .sup.1H NMR (400 MHz, CDCl.sub.3) 7.73-7.64 (m, 1H, H.sub.ar), 7.56-7.47 (m, 3H, H.sub.ar), 7.36-7.33 (m, 4H, H.sub.ar), 7.31-7.26 (m, 9H, H.sub.ar), 7.22 (d, J=7.9 Hz, 3H, H.sub.ar), 6.82 (d, J=8.5 Hz, 2H, H.sub.ar), 6.71 (t, J=9.1 Hz, 1H, H.sub.ar), 6.41 (d, J=15.8 Hz, 1H), 6.05 (d, J.sub.1=8.5 Hz, J.sub.2=15.7 Hz, 1H), 5.27 (d, J=7.1 Hz, 1H, CH), 3.79 (s, 3H, CH.sub.3). .sup.13C NMR (100 MHz, CDCl.sub.3) 159.04, 153.35 (d, J=22.7 Hz), 144.59, 143.54, 136.75 (d, J=14.5 Hz), 132.22, 132.12, 132.04, 131.59 (d, J=8.8 Hz), 130.85, 130.00, 128.93, 127.98 (d, J=1.8 Hz), 127.75, 127.35, (d, J=12.4 Hz), 124.47 (d, J=15.4 Hz), 113.86, 75.46, 55.31. .sup.31P NMR (162 MHz, CDCl.sub.3) 51.80 HRMS (ESI) calculated [M+H].sup.+ for C.sub.34H.sub.30OP: 501.1978. found: 501.1995.

(147) FTIR (cm.sup.1) 3861, 3744, 3678, 3619, 3060, 2981, 1736, 1647. 1608, 1469, 1434, 1370, 1249, 119 5, 1113, 1079, 986, 872, 833, 745.

Example 26: Synthesis of 3-(4-Chlorophenyl)-5,6-dimethyl-1,1,1-triphenyl-1,3-dihydro-15 benzo[c][1,2]oxaphosphole (4z)

(148) ##STR00075##

(149) Following the general procedure, treatment of 4,5-dimethyl-2-(trimethylsilyl)phenyl trifluoromethanesulfonate 1a (0.196 g, 0.60 mmol) and 4-chlorobenzaldehyde 1b (0.105 g, 0.75 mmol) with triphenylphosphine 1c (0.131 g, 0.50 mmol) in the presence of KF (0.070 g, 1.2 mmol) and 18-crown-6 (0.317 g, 1.2 mmol) in THF (3.0 mL) at 10 C. to rt for 12 h followed by flash column chromatography (Pet. ether/EtOAc=40/60) of the crude reaction mixture using silica gel afforded 3-(4-chlorophenyl)-5,6-dimethyl-1,1,1-triphenyl-1,3-dihydro-1.sup.5-benzo[c][1,2]oxaphosphole 4z as a white solid (0.163 g, 64% yield).

(150) R.sub.f (EtOAc): 0.39; .sup.1H NMR (400 MHz, CDCl.sub.3) 7.42-7.37 (m, 6H), 7.32-7.26 (m, 9H), 7.22 (d, J=8.1 Hz, 2H), 7.07 (d, J=7.8 Hz, 2H), 6.98 (bs, 1H), 6.59 (d, J=11.3 Hz, 1H), 5.61 (s, 1H, CH), 2.27 (s, 3H), 2.13 (s, 3H). .sup.13C NMR (100 MHz, CDCl.sub.3) 151.96 (d, J=21.2 Hz), 144.07, 143.33, 143.01, 142.08 (d, J=3.1 Hz), 137.26 (d, J=14.9 Hz), 135.96 (d, J=14.8 Hz), 132.72, 131.35 (d, J=8.6 Hz), 129.06, 128.60, 127.99 (d, J=1.7 Hz), 127.38 (d, J=12.3 Hz), 125.84 (d, J=16.2 Hz), 76.24, 20.15, 20.11. .sup.31P NMR (162 MHz, CDCl.sub.3) 51.37 HRMS (ESI) calculated [M+H].sup.+ for C.sub.33H.sub.29ClOP: 507.1639. found: 507.1643. FTIR (cm.sup.1) 3925, 3861, 3829, 3648, 3566, 3058, 2979, 2360, 1835, 1741, 1707, 1647, 1485, 1436, 1265, 1225, 1081, 1018, 810, 745, 662.

Example 27: Synthesis of 3-(4-Chlorophenyl)-5,6-difluoro-1,1,1-triphenyl-1,3-dihydro-15-benzo[c] [1,2] oxaphosphole (4aa)

(151) ##STR00076##

(152) Following the general procedure, treatment of 4,5-difluoro-2-(trimethylsilyl)phenyl trifluoromethanesulfonate 1a (0.201 g, 0.60 mmol) and 4-chlorobenzaldehyde 1b (0.105 g, 0.75 mmol) with triphenylphosphine 1c (0.131 g, 0.50 mmol) in the presence of KF (0.070 g, 1.20 mmol) and 18-crown-6 (0.317 g, 1.20 mmol) in THF (3.0 mL) at 10 C. to rt for 12 h followed by flash column chromatography (Pet. ether/EtOAc=40/60) of the crude reaction mixture using silica gel afforded 3-(4-chlorophenyl)-5,6-difluoro-1,1,1-triphenyl-1,3-dihydro-1.sup.5-benzo[c][1,2]oxaphosphole 4aa as a white solid (0.193 g, 75% yield).

(153) R.sub.f (EtOAc): 0.48; .sup.1H NMR (400 MHz, CDCl.sub.3) 7.37-7.32 (m, 15H, H.sub.ar), 7.22 (d, J=8.0 Hz, 2H, H.sub.ar), 7.04 (d, J=8.0 Hz, 2H, H.sub.ar), 6.93 (t, J=6.9 Hz, 1H, H.sub.ar), 6.62-6.55 (m, 1H, H.sub.ar), 5.43 (s, 1H, CH). .sup.13C NMR (100 MHz, CDCl.sub.3) 153.33 (d, J=259.8 Hz), 153.20 (d, J=257.5 Hz), 151.16-150.81 (m), 150.62 (d, J=5.4 Hz), 148.51 (d, J.sub.1=12.9 Hz, J.sub.2=22.0 Hz), 142.99, 141.78, 133.46, 131.39 (d, J=9.0 Hz), 129.03, 128.62 (d, J=7.2 Hz), 127.93, 127.70 (d, J=12.5 Hz), 124.57 (t, J=18.7 Hz), 113.13 (t, J=18.4 Hz), 75.45. .sup.31P NMR (162 MHz, CDCl.sub.3) 51.78 HRMS (ESI) calculated [M+H].sup.+ for C.sub.31H.sub.23ClF.sub.2OP: 515.1138. found: 515.1165. FTIR (cm.sup.1) 3894, 3861, 3744, 3678, 2928, 2361, 1741, 1693, 1647, 1614, 1516, 1488, 1430, 1293, 1215, 1084, 1006, 898, 742.

Example 28: Synthesis of 3-(4-Chlorophenyl)-1,1,1-triphenyl-1,3-dihydro-15-[1,3]dioxolo [4,5:4,5] benzo[1,2-c][1,2]oxaphosphole (4ab)

(154) ##STR00077##

(155) Following the general procedure, treatment of 6-(trimethylsilyl)benzo[d][1,3]dioxol-5-yl trifluoromethanesulfonate 1a (0.206 g, 0.60 mmol) and 4-chlorobenzaldehyde 1b (0.105 g, 0.75 mmol) with triphenylphosphine 1c (0.131 g, 0.50 mmol) in the presence of KF (0.070 g, 1.20 mmol) and 18-crown-6 (0.317 g, 1.20 mmol) in THF (3.0 mL) at 10 C. to rt for 12 h followed by flash column chromatography (Pet. ether/EtOAc=40/60) of the crude reaction mixture using silica gel afforded 3-(4-chlorophenyl)-1,1,1-triphenyl-1,3-dihydro-1.sup.5-[1,3]dioxolo[4,5:4,5]benzo[1,2-c][1,2] oxaphosphole 4ab as a white solid (0.201 g, 77% yield).

(156) R.sub.f (EtOAc): 0.32; .sup.1H NMR (400 MHz, CDCl.sub.3) 7.40-7.26 (m, 6H, H.sub.ar), 7.32 (bs, 9H, H.sub.ar), 7.22-7.20 (m, 2H, H.sub.ar), 7.06-7.04 (m, 2H, H.sub.ar), 6.59 (bs, 1H, H.sub.ar), 6.21-6.17 (m, 1H, H.sub.ar), 5.97 (d, J=6.2 Hz, 2H, CH.sub.2), 5.50 (s, 1H, CH). .sup.13C NMR (100 MHz, CDCl.sub.3) 151.94, 150.23 (d, J=23.0 Hz), 147.84 (d, J=22.4 Hz), 143.31, 142.73, 142.25, 133.02, 131.41 (d, J=8.9 Hz), 129.10, 128.37 (d, J=9.3 Hz), 127.57 (d, J=12.5 Hz), 120.74, 119.34, 114.56 (d, J=19.3 Hz), 104.85 (d, J=19.1 Hz), 102.28, 76.16. .sup.31P NMR (162 MHz, CDCl.sub.3) 49.02 HRMS (ESI) calculated [M+H].sup.+ for C.sub.32H.sub.25ClO.sub.3P: 523.1224. found: 523.1228. FTIR (cm.sup.1) 3829, 3744, 3619, 3061, 2981, 2899, 1736, 1609, 1469, 1432, 1250, 1079, 986, 832, 745, 661.

Example 29: Synthesis of 3-(4-Chlorophenyl)-1,1,1-triphenyl-3,5,6,7-tetrahydro-1H-15-indeno[5,6-c][1,2]oxaphosphole (4ac)

(157) ##STR00078##

(158) Following the general procedure, treatment of 6-(trimethylsilyl)-2,3-dihydro-1H-inden-5-yl trifluoromethanesulfonate 1a (0.201 g, 0.60 mmol) and 4-chlorobenzaldehyde 1b (0.105 g, 0.75 mmol) with triphenylphosphine 1c (0.131 g, 0.50 mmol) in the presence of KF (0.070 g, 1.20 mmol) and 18-crown-6 (0.317 g, 1.20 mmol) in THF (3.0 mL) at 10 C. to rt for 12 h followed by flash column chromatography (Pet. ether/EtOAc=40/60) of the crude reaction mixture using silica gel afforded 3-(4-chlorophenyl)-1,1,1-triphenyl-3,5,6,7-tetrahydro-1H-1.sup.5-indeno[5,6-c][1,2]oxaphosphole 4ac as a white solid (0.204 g, 79% yield).

(159) R.sub.f (EtOAc): 0.43; .sup.1H NMR (400 MHz, CDCl.sub.3) 7.42-7.37 (m, 6H, H.sub.ar), 7.31-7.27 (m, 9H, H.sub.ar), 7.21 (d, J=8.3 Hz, 2H, H.sub.ar), 7.08 (d, J=8.4 Hz, 2H, H.sub.ar), 7.03 (b s, 1H, H.sub.ar), 6.69 (d, J=11.3 Hz, 1H, H.sub.ar), 5.59 (s, 1H, CH), 2.94-2.83 (m, 2H, CH.sub.2), 2.77 (t, J=7.3 Hz, 2H, CH.sub.2), 2.12-2.04 (m, 2H, CH.sub.2). .sup.13C NMR (100 MHz, CDCl.sub.3) 152.89 (d, J=22.5 Hz), 150.18 (d, J=2.9 Hz), 144.23, 144.19, 144.08, 143.42, 143.12, 132.74, 131.84 (d, J=15.4 Hz), 131.34 (d, J=8.9 Hz), 129.10, 128.29, 127.96 (d, J=1.8 Hz), 127.39 (d, J=12.3 Hz), 120.53 (d, J=17.0 Hz), 76.37, 32.71, 32.47, 25.85. .sup.31P NMR (162 MHz, CDCl.sub.3) 51.78 HRMS (ESI) calculated [M+H].sup.+ for C.sub.34H.sub.29ClOP: 519.1639. found: 519.1638. FTIR (cm.sup.1) 3893, 3843, 3743, 3565, 3059, 3008, 2361, 1845, 1740, 1693, 1546, 1485, 1436, 1398, 1268, 1195, 1111, 1034, 803, 694, 633.

Example 30: Synthesis of 1-(4-Chlorophenyl)-3,3,3-triphenyl-1,3-dihydro-35-naphtho[2,1-c][1,2] oxaphosphole (4ad)

(160) ##STR00079##

(161) Following the general procedure, treatment of 2-(trimethylsilyl)naphthalen-1-yl trifluoromethanesulfonate 1a (0.209 g, 0.60 mmol) and 4-chlorobenzaldehyde 1b (0.105 g, 0.75 mmol) with triphenylphosphine 1c (0.131 g, 0.50 mmol) in the presence of KF (0.070 g, 1.20 mmol) and 18-crown-6 (0.317 g, 1.20 mmol) in THF (3.0 mL) at 10 C. to rt for 12 h followed by flash column chromatography (Pet. ether/EtOAc=40/60) of the crude reaction mixture using silica gel afforded 1-(4-chlorophenyl)-3,3,3-triphenyl-1,3-dihydro-3.sup.5-naphtho[2,1-c][1,2]oxaphosphole 4ad as a white solid (0.181 g, 68% yield).

(162) R.sub.f (EtOAc): 0.45; .sup.1H NMR (400 MHz, CDCl.sub.3) 7.81 (d, J=8.2 Hz, 1H, H.sub.ar), 7.71 (d, J=8.3 Hz, 1H, H.sub.ar), 7.50-7.42 (m, 8H, H.sub.ar), 7.36 (d, J=8.2 Hz, 2H, H.sub.ar), 7.27-7.22 (m, 10H, H.sub.ar), 7.19 (d, J=7.5 Hz, 1H, H.sub.ar), 7.05 (d, J=8.6 Hz, 1H, H.sub.ar), 6.91 (t, J=7.3 Hz, 1H, H.sub.ar), 6.23 (d, J=8.2 Hz, 1H, H.sub.ar). .sup.13C NMR (100 MHz, CDCl.sub.3) 147.85, 147.00, 142.93, 141.47 (d, J=2.0 Hz), 134.05 (d, J=8.0 Hz), 133.55, 132.21 (d, J=11.3 Hz), 131.83 (d, J=9.9 Hz), 131.46, 128.79, 128.56, 128.32, 127.47 (d, J=12.1 Hz), 125.29, 124.81, 121.00, 74.08. .sup.31P NMR (162 MHz, CDCl.sub.3) 49.36 HRMS (ESI) calculated [M+H].sup.+ for C.sub.35H.sub.27ClOP: 529.1483. found: 529.1483. FTIR (cm.sup.1) 3894, 3648, 3619, 3011, 2362, 1836, 1707, 1648, 1646, 1467, 1429, 1282, 1217, 1009, 743, 668.

Example 31: Synthesis of 3-(4-Chlorophenyl)-5-methyl-1,1,1-triphenyl-1,3-dihydro-15-benzo[c][1,2] oxaphosphole & 3-(4-Chlorophenyl)-6-methyl-1,1,1-triphenyl-1,3-dihydro-15-benzo[c][1,2]oxaphosphole (4ae & 4ae)

(163) ##STR00080##

(164) Following the general procedure, treatment of 5-methyl-2-(trimethylsilyl)phenyl trifluoromethanesulfonate 1a (0.189 g, 0.60 mmol) and 4-chlorobenzaldehyde 1b (0.105 g, 0.75 mmol) with triphenylphosphine 1c (0.131 g, 0.50 mmol) in the presence of KF (0.070 g, 1.20 mmol) and 18-crown-6 (0.317 g, 1.20 mmol) in THF (3.0 mL) at 10 C. to rt for 12 h followed by flash column chromatography (Pet. ether/EtOAc=40/60) of the crude reaction mixture using silica gel afforded 3-(4-chlorophenyl)-5-methyl-1,1,1-triphenyl-1,3-dihydro-1.sup.5-benzo[c] [1,2] oxaphosphole 4ae and 3-(4-chlorophenyl)-6-methyl-1,1,1-triphenyl-1,3-dihydro-1.sup.5-benzo[c][1,2]oxaphosphole 4ae as inseparable mixture of regioisomers in 1:1 ratio as a white solid (0.229 g, 93% yield, regioisomeric ratio was determined by .sup.1H NMR analysis of crude reaction mixture).

(165) R.sub.f (EtOAc): 0.45; .sup.1H NMR (500 MHz, CDCl.sub.3) 7.42-7.36 (m, 6H, H.sub.ar), 7.34-7.29 (m, 10H, H.sub.ar), 7.25-7.22 (m, 2H, H.sub.ar), 7.12-7.06 (m, 3H, H.sub.ar), 6.78-6.73 (m, H.sub.ar), 6.67-6.64 (m, H.sub.ar), 5.61-5.59 (m, 1H, CH), 2.29 (s, CH.sub.3), 2.25 (s, CH.sub.3). .sup.13C NMR (125 MHz, CDCl.sub.3) 154.35 (d, J=21.6 Hz), 131.35 (d, J=21.3 Hz), 143.93 (d, J=5.2 Hz), 143.25, 143.21, 143.11, 142.84, 137.06 (d, J=14.3 Hz), 136.84 (d, J=14.4 Hz), 136.53 (d, J=14.9 Hz), 133.43 (d, J=2.7 Hz), 132.87, 131.42 (d, J=8.8 Hz), 129.17, 129.11, 128.76, 128.61, 128.36 (d, J=2.2 Hz), 128.10, 127.77, 127.46 (d, J=12.4 Hz), 125.64, 125.52, 125.36, 124.06, 124.50, 124.28, 76.37, 76.15, 21.47. .sup.31P NMR (203 MHz, CDCl.sub.3) 50.95 & 51.49. HRMS (ESI) calculated [M+H].sup.+ for C.sub.32H.sub.27ClOP: 493.1483. found: 493.1480. FTIR (cm.sup.1) 3054.42, 1733, 1659, 1589, 1484, 1435, 1402, 1255, 1184, 1116, 1087, 1073, 1053, 1028, 1013, 997, 966, 933, 848, 822, 794, 748, 721, 691, 665, 633.

Example 32: Synthesis of 3-(4-Chlorophenyl)-5-fluoro-1,1,1-triphenyl-1,3-dihydro-15-benzo[c][1,2]oxaphosphole & 3-(4-Chlorophenyl)-6-fluoro-1,1,1-triphenyl-1,3-dihydro-15-benzo[c][1,2] oxaphosphole (4af & 4af)

(166) ##STR00081##

(167) Following the general procedure, treatment of 4-fluoro-2-(trimethylsilyl)phenyl trifluoromethanesulfonate 1a (0.189 g, 0.60 mmol) and 4-chlorobenzaldehyde 1b (0.105 g, 0.75 mmol) with triphenylphosphine 1c (0.131 g, 0.50 mmol) in the presence of KF (0.070 g, 1.20 mmol) and 18-crown-6 (0.317 g, 1.20 mmol) in THF (3.0 mL) at 10 C. to rt for 12 h followed by flash column chromatography (Pet. ether/EtOAc=40/60) of the crude reaction mixture using silica gel afforded 3-(4-chlorophenyl)-5-fluoro-1,1,1-triphenyl-1,3-dihydro-1.sup.5-benzo[c] [1,2] oxaphosphole 4af and 3-(4-chlorophenyl)-6-fluoro-1,1,1-triphenyl-1,3-dihydro-1.sup.5-benzo[c] [1,2]oxaphosphole 4af as inseparable mixture of regioisomers in 3:1 ratio as a white solid (0.216 g, 87% yield, regioisomeric ratio was determined by .sup.1H NMR analysis of crude reaction mixture).

(168) R.sub.f (EtOAc): 0.53; .sup.1H NMR (500 MHz, CDCl.sub.3) 7.45-7.38 (m, 4H, H.sub.ar), 7.37-7.34 (m, 11H, H.sub.ar), 7.27 (d, J=8.3 Hz, 3H, H.sub.ar), 7.12-7.08 (m, 2H, H.sub.ar), 6.98-6.80 (m, 2H, H.sub.ar), 5.56 (s, 1H, CH). .sup.13C NMR (125 MHz, CDCl.sub.3) 165.72 (d, J.sub.C-F=256.2 Hz), 157.26 (dd, J.sub.1=7.9 Hz, J.sub.2=24.8 Hz), 143.58, 142.47, 142.28, 138.83-138.62 (m), 133.27, 131.41, 131.34, 129.05, 128.29, 127.59 (d, J=12.4 Hz), 123.37, 122.63-122.31 (m), 115.10 (dd, J.sub.1=17.2 Hz, J.sub.2=20.4 Hz), 111.66 (t, J=21.3 Hz), 76.00. .sup.31P NMR (203 MHz, CDCl.sub.3) 52.59. Representative Peaks of Minor Isomer: .sup.1H NMR 7.22-7.14 (m), 6.56-6.50 (m), 5.51 (s). .sup.13C NMR 149.33 (d, J=20.0 Hz), 143.34, 142.73, 133.21, 131.47, 129.19, 128.58, 128.38, 125.86-125.66 (m), 124.48, 119.80 (d, J=23.4 Hz), 75.64. .sup.31P NMR 52.23. HRMS (ESI) calculated [M+H].sup.+ for C.sub.31H.sub.24ClFOP: 497.1232. found: 497.1232. FTIR (cm.sup.1) 3843, 3744, 3678, 3648, 3012, 2361, 1741, 1693, 1597, 1483, 1217, 1086, 1053, 955, 830, 742, 697, 636.

Example 33: Synthesis of 3-(4-Chlorophenyl)-1,1,1-tri-p-tolyl-1,3-dihydro-15-benzo[c][1,2] oxaphosphole (4ag)

(169) ##STR00082##

(170) Following the general procedure, treatment of 2-(trimethylsilyl)phenyl trifluoromethanesulfonate 1a (0.179 g, 146 L, 0.60 mmol) and 4-chlorobenzaldehyde 1b (0.105 g, 0.75 mmol) with tri-p-tolylphosphane 1c (0.152 g, 0.50 mmol) in the presence of KF (0.070 g, 1.20 mmol) and 18-crown-6 (0.317 g, 1.20 mmol) in THF (3.0 mL) at 10 C. to rt for 12 h followed by flash column chromatography (Pet. ether/EtOAc=40/60) of the crude reaction mixture using silica gel afforded 3-(4-chlorophenyl)-1,1,1-tri-p-tolyl-1,3-dihydro-1.sup.5-benzo[c][1,2]oxaphosphole 4ag as a white solid (0.193 g, 74% yield).

(171) R.sub.f (EtOAc): 0.30; .sup.1H NMR (400 MHz, CDCl.sub.3) 7.47 (t, J=5.5 Hz, 1H, H.sub.ar), 7.32-7.27 (m, 6H, H.sub.ar), 7.24-7.20 (m, 4H, H.sub.ar), 7.15-7.11 (m, 8H, H.sub.ar), 6.90 (dd, =8.1 Hz, J.sub.2=10.9 Hz, 1H, H.sub.ar), 5.56 (s, 1H, CH), 2.39 (s, 9H, 3CH.sub.3). .sup.13C NMR (100 MHz, CDCl.sub.3) 153.79 (d, J=20.1 Hz), 143.18, 140.10, 139.02, 137.97 (d, J=1.8 Hz), 136.49 (d, J=14.5 Hz), 132.77, 132.11, 131.59 (d, J=9.2 Hz), 129.38, 129.23, 128.23 (d, J=6.5 Hz), 128.07, 127.24 (d, J=14.1 Hz), 124.86 (d, J=15.1 Hz), 75.81, 21.36. .sup.31P NMR (162 MHz, CDCl.sub.3) 49.23 HRMS (ESI) calculated [M+H].sup.+ for C.sub.34H.sub.31ClOP: 521.1796. found: 521.1797. FTIR (cm.sup.1) 3743, 3056, 2983, 1733, 1589, 1484, 1437, 1317, 1245, 1184, 1111, 1051, 846, 813, 745, 694. 662.

Example 34: Synthesis of 3-(4-Chlorophenyl)-1,1,1-tris(4-methoxyphenyl)-1,3-dihydro-15-benzo[c][1,2] oxaphosphole (4ah)

(172) ##STR00083##

(173) Following the general procedure, treatment of 2-(trimethylsilyl)phenyl trifluoromethanesulfonate 1a (0.179 g, 146 L, 0.60 mmol) and 4-chlorobenzaldehyde 1b (0.105 g, 0.75 mmol) with tris(4-methoxyphenyl)phosphane 1c (0.176 g, 0.50 mmol) in the presence of KF (0.070 g, 1.20 mmol) and 18-crown-6 (0.317 g, 1.20 mmol) in THF (3.0 mL) at 10 C. to rt for 12 h followed by flash column chromatography (EtOAc) of the crude reaction mixture using silica gel afforded 3-(4-chlorophenyl)-1,1,1-tris(4-methoxyphenyl)-1,3-dihydro-1.sup.5-benzo[c][1,2]oxaphosphole 4ah as a white solid (0.166 g, 58% yield).

(174) R.sub.f (EtOAc): 0.23; .sup.1H NMR (500 MHz, CDCl.sub.3) 7.65 (t, J=7.0 Hz, 2H, H.sub.ar), 7.35-7.31 (m, 7H, H.sub.ar), 7.03-6.99 (m, 3H, H.sub.ar), 6.92-6.91 (m, 6H, H.sub.ar), 6.76 (bs, 2H, H.sub.ar), 5.57 (s, 1H, CH), 3.82 (s, 9H, 3CH.sub.3). .sup.13C NMR (125 MHz, CDCl.sub.3) 162.34 (d, J=8.8 Hz), 150.63, 141.46, 135.99 (d, J=13.3 Hz), 134.89 (d, J=7.3 Hz), 133.88, 132.73, 129.10, 128.40, 128.29, 128.04, 114.60, 73.86, 55.61. .sup.31P NMR (203 MHz, CDCl.sub.3) 40.79. HRMS (ESI) calculated [M+H].sup.+ for C.sub.34H.sub.31ClO.sub.4P: 569.1643. found: 569.1646. FTIR (cm.sup.1) 3894, 3678, 3619, 3018, 2362, 1741, 1693, 1596, 1464, 1264, 1267, 1217, 1110, 1027, 740, 667.

Example 35: Synthesis of 3-(4-Chlorophenyl)-1,1,1-tri-o-tolyl-1,3-dihydro-15-benzo[c][1,2]oxaphosphole (4ai)

(175) ##STR00084##

(176) Following the general procedure, treatment of 2-(trimethylsilyl)phenyl trifluoromethanesulfonate 1a (0.179 g, 146 L, 0.60 mmol) and 4-bromobenzaldehyde 1b (0.137 g, 0.75 mmol) with tri-o-tolylphosphane 1c (0.152 g, 0.50 mmol) in the presence of KF (0.070 g, 1.20 mmol) and 18-crown-6 (0.317 g, 1.20 mmol) in THF (3.0 mL) at 10 C. to rt for 12 h followed by flash column chromatography (EtOAc) of the crude reaction mixture using silica gel afforded 3-(4-chlorophenyl)-1,1,1-tri-o-tolyl-1,3-dihydro-1.sup.5-benzo[c][1,2]oxaphosphole 4ai as a white solid (0.167 g, 64% yield).

(177) R.sub.f (EtOAc): 0.17; .sup.1H NMR (500 MHz, CDCl.sub.3) 8.12-8.07 (m, 1H, H.sub.ar), 8.03 (t, J=6.4 Hz, 1H, H.sub.ar), 7.92-7.89 (m, 1H, H.sub.ar), 7.72-7.69 (m, 2H, H.sub.ar), 7.66-7.59 (m, 4H, H.sub.ar), 7.48-7.46 (m, 2H, H.sub.ar), 7.43-7.40 (m, 1H, H.sub.ar), 7.34-7.30 (m, 2H, H.sub.ar), 6.95-6.90 (m, 1H, H.sub.ar), 6.86 (d, J=8.1 Hz, 2H, H.sub.ar), 6.42 (d, J=7.9 Hz, 2H, H.sub.ar), 5.58 (d, J=3.5 Hz, 1H, H.sub.ar), 5.31 (d, J=4.0 Hz, 1H, CH), 1.82 (s, 6H, 2CH.sub.3), 1.75 (s, 3H, CH.sub.3). .sup.13C NMR (125 MHz, CDCl.sub.3) 148.45 (d, J=8.3 Hz), 144.25 (d, J=8.6 Hz), 143.68 (d, J=8.5 Hz), 142.98 (d, J=9.2 Hz), 139.12, 136.67 (d, J=12.6 Hz), 135.76-135.68 (m), 135.55-135.49 (m), 135.39, 135.33, 134.76 (d, J=13.8 Hz), 134.39 (d, J=11.2 Hz), 133.92 (d, J=11.5 Hz), 133.56 (d, J=10.9 Hz), 133.25 (d, J=10.4 Hz), 133.07, 129.76 (d, J=13.0 Hz), 128.97 (d, J=13.3 Hz), 128.65, 128.59, 128.26, 128.06, 127.9 (d, J=12.9 Hz), 127.72, 121.89, 119.34, 116.33 (d, J=11.8 Hz), 115.84, 115.68 (d, J=10.8 Hz), 115.16, 114.73, 114.05, 72.19 (d, J=4.5 Hz), 23.19, 23.15, 22.86. .sup.31P NMR (203 MHz, CDCl.sub.3) 22.33 HRMS (ESI) calculated [M+H].sup.+ for C.sub.34H.sub.31ClOP: 521.1796. found: 521.1795. FTIR (cm.sup.1) 3893, 3843, 3678, 3619, 3019. 2362, 1836, 1741, 1693, 1646, 1516, 1464, 1215, 741, 668.

Example 36: Synthesis of 3-(4-Chlorophenyl)-1,1-diphenyl-1-(p-tolyl)-1,3-dihydro-15-benzo[c] [1,2] oxaphosphole (4aj)

(178) ##STR00085##

(179) Following the general procedure, treatment of 2-(trimethylsilyl)phenyl trifluoromethanesulfonate 1a (0.179 g, 146 L, 0.60 mmol) and 4-chlorobenzaldehyde 1b (0.105 g, 0.75 mmol) with diphenyl(p-tolyl)phosphane 1c (0.138 g, 0.50 mmol) in the presence of KF (0.070 g, 1.20 mmol) and 18-crown-6 (0.317 g, 1.20 mmol) in THF (3.0 mL) at 10 C. to rt for 12 h followed by flash column chromatography (Pet. ether/EtOAc=40/60) of the crude reaction mixture using silica gel afforded 3-(4-chlorophenyl)-1,1-diphenyl-1-(p-tolyl)-1,3-dihydro-1.sup.5-benzo[c][1,2]oxaphosphole 4aj as a white solid (0.198 g, 80% yield).

(180) R.sub.f (EtOAc): 0.37; .sup.1H NMR (400 MHz, CDCl.sub.3) 7.49-7.45 (m, 1H, H.sub.ar), 7.40-7.35 (m, 4H, H.sub.ar), 7.32-7.28 (m, 8H, H.sub.ar), 7.24-7.21 (m, 4H, H.sub.ar), 7.14-7.12 (m, 2H, H.sub.ar), 7.08 (d, J=8.2 Hz, 2H, H.sub.ar), 6.88 (dd, J.sub.1=8.4 Hz, J.sub.2=11.0 Hz, 1H, H.sub.ar), 5.59 (s, 1H, CH), 2.37 (s, 3H, CH.sub.3). .sup.13C NMR (100 MHz, CDCl.sub.3) 153.84 (d, J=20.1 Hz), 142.99, 138.26 (d, J=2.2 Hz), 136.55 (d, J=14.4 Hz), 132.88, 132.28 (d, J=2.8 Hz), 131.85 (d, J=9.5 Hz), 131.47, 131.37 (d, J=2.9 Hz), 131.26, 129.18, 128.33, 128.27, 128.14, 127.49 (d, J=11.9 Hz), 127.30, 124.91 (d, J=15.1 Hz), 76.05, 21.38. .sup.31P NMR (162 MHz, CDCl.sub.3) 44.49. HRMS (ESI) calculated [M+H].sup.+ for C.sub.32H.sub.27ClOP: 493.1483. found: 493.1525. FTIR (cm.sup.1) 3861, 3649, 3062, 3006, 2319, 1740, 1693, 1596, 1437, 1399, 1259, 1222, 1185, 1017, 812, 743, 664.

Example 37: Synthesis of 1,1,1-Tributyl-3-(4-chlorophenyl)-1,3-dihydro-15-benzo[c] [1,2] oxaphosphole (4ak)

(181) ##STR00086##

(182) Following the general procedure, treatment of 2-(trimethylsilyl)phenyl trifluoromethanesulfonate 1a (0.179 g, 146 L, 0.60 mmol) and 4-chlorobenzaldehyde 1b (0.105 g, 0.75 mmol) with tri-n-butylphosphine 1c (0.101 g, 125 L, 0.50 mmol) in the presence of KF (0.070 g, 1.20 mmol) and 18-crown-6 (0.317 g, 1.20 mmol) in THF (3.0 mL) at 10 C. to rt for 12 h followed by flash column chromatography (Pet. ether/EtOAc=40/60) of the crude reaction mixture using silica gel afforded 1,1,1-tributyl-3-(4-chlorophenyl)-1,3-dihydro-1.sup.5-benzo[c][1,2]oxaphosphole 4ak as a white solid (0.167 g, 79% yield).

(183) R.sub.f (EtOAc): 0.21; .sup.1H NMR (400 MHz, CDCl.sub.3) 7.68 (dd, J.sub.1=7.6 Hz, J.sub.2=13.4 Hz, 1H, H.sub.ar), 7.59-7.50 (m, 2H, H.sub.ar), 7.25 (d, J=8.3 Hz, 2H, H.sub.ar), 7.16 (d, J=8.5 Hz, 3H, H.sub.ar), 6.05 (s, 1H, CH), 2.47-2.44 (m, 6H, 3CH.sub.2), 1.50-1.21 (m, 12H, 6CH.sub.2), 0.84 (t, J=6.5 Hz, 9H, 3CH.sub.3). .sup.13C NMR (100 MHz, CDCl.sub.3) 143.38 (d, J=6.4 Hz), 141.37, 134.33 (d, J=8.8 Hz), 133.95 (d, J=2.2 Hz), 133.75, 131.52 (d, J=10.4 Hz), 128.85, 128.68 (d, J=12.7 Hz), 115.78, 115.00, 73.47 (d, J=1.8 Hz), 24.25 (d, J=4.1 Hz), 23.63 (d, J=16.3 Hz), 21.65 (d, J=50.3 Hz), 13.36. .sup.31P NMR (162 MHz, CDCl.sub.3) 32.97 HRMS (ESI) calculated [M+H].sup.+ for C.sub.25H.sub.37ClOP: 419.2265. found: 419.2265. FTIR (cm.sup.1) 3843, 3648, 3619, 3010, 2873, 2361, 1817, 1741, 1647, 1463, 1351, 1251, 1222, 1030, 949, 854, 742, 637.