Cyclopropane skeleton monophosphine ligands, palladium complexes thereof, preparation methods and application

Abstract

The present invention relates to cyclopropane skeleton monophosphine ligands and preparation methods for palladium complexes thereof and an application. Specifically, trans-diaryl substituted cyclopropane skeleton monophosphine ligands are synthesized after trans-1,2-diaryl ethylene undergoing the steps of cyclopropanation reaction, debromination reaction, substitution reaction, and the like. Palladium complexes prepared by coordinating the cyclopropane skeleton monophosphine ligands with a palladium salt show very high activity in catalyzing CN bond coupling reactions, and have good application prospects.

Claims

1. Cyclopropane skeleton monophosphine ligands, having the following structural formula as I: ##STR00078## where R.sup.1 and R.sup.2 are phenyl or substituted phenyl, R.sup.3 and R.sup.4 are C.sub.1-C.sub.8 alkyl, and R.sup.5 is a hydrogen atom, R.sup.1, R.sup.2, R.sup.3, R.sup.4, and R.sup.5 being same or different, wherein in the substituted phenyl, a substituent is one or more of C.sub.1-C.sub.8 alkyl, C.sub.1-C.sub.8 alkoxy; if R.sup.1 and R.sup.2 are substituted phenyl, the number of substituents is 1 or 2.

2. The cyclopropane skeleton monophosphine ligands according to claim 1, wherein alkyl in the C.sub.1-C.sub.8 alkyl or in the C.sub.1-C.sub.8 alkoxy is methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-amyl, isopentyl, neopentyl, sec-pentyl, tert-pentyl, n-hexyl, isohexyl, neohexyl, sec-hexyl, tert-hexyl, n-heptyl, isoheptyl, neoheptyl, sec-heptyl, tert-heptyl, n-octyl, isooctyl, neooctyl, sec-octyl, or tert-octyl.

3. The cyclopropane skeleton monophosphine ligands according to claim 2, having the following structural formulas as I-a, I-b, I-c or I-d: ##STR00079##

4. A preparation method for cyclopropane skeleton monophosphine ligands according to claim 1, comprising the following two routes: when R.sup.5=H, a synthetic route being as follows: performing cyclopropanation reaction of trans-1,2-diaryl ethylene with bromoform in the presence of NaOH and a phase transfer catalyst benzyltriethylammonium chloride (TEBAC) to prepare a gem-dibromocyclopropane intermediate III; and performing protonation of the gem-dibromocyclopropane intermediate III after being subjected to bromo-lithium exchange with n-butyllithium to prepare a monobromocyclopropane intermediate IV; and undergoing substitution reaction with R.sup.3R.sup.4PCI by the monobromocyclopropane intermediate IV after bromo-lithium exchange with n-butyllithium, to prepare a cyclopropane skeleton monophosphine ligand I, with a reaction formula as follows: ##STR00080##

5. Adducts of cyclopropane skeleton monophosphine ligands according to claim 1 and borane, having the following structural formula as II: ##STR00081##

6. A preparation method for adducts according to claim 5, comprising the following steps: reacting cyclopropane skeleton monophosphine ligands with a solution of borane in tetrahydrofuran (THF) to produce corresponding adducts, with the following formula: ##STR00082##

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 shows a single-crystal structure of an adduct II-c of a cyclopropane skeleton monophosphine ligand I and borane; and

(2) FIG. 2 shows a single-crystal structure of a palladium complex VI-h of the cyclopropane skeleton monophosphine ligand I.

DETAILED DESCRIPTION

(3) The following examples help to further understand the present invention, but are not the limitation on the scope of the above-described subjects of the present invention, and any technology realized on the basis of the above-described content of the present invention is within the scope of the present invention.

(4) General Description:

(5) Abbreviations are used in the following examples, which have the following meanings:

(6) Me is short for methyl, Et is short for ethyl, Bu is short for tert-butyl, Bu is short for n-butyl, Ph is short for phenyl, THF is short for tetrahydrofuran, Et.sub.2O is short for diethyl ether, CHBr.sub.3 is short for bromoform, TEBAC is short for benzyltriethylammonium chloride, PE is short for petroleum ether, EA is short for ethyl acetate, Ar is short for argon, CDCl.sub.3 is short for deuterochloroform, COD is short for 1,5-cyclooctadiene, TMS is short for trimethylsilane substituent; dba is short for dibenzylideneacetone, OAc is short for acetate, and TFA is short for trifluoroacetate.

(7) eq. is short for equivalent, rt is short for room temperature, TLC is short for thin layer chromatography, NMR is short for nuclear magnetic resonance, HRMS is short for high resolution mass spectrometry, GC is short for gas chromatography, turnover frequency=amount of substance of converted raw materials/amount of substance of initial raw materials, and turnover number=amount of substance of target product/amount of substance of palladium catalyst.

(8) The solvent used is purified by standard operations and dried before use; and the reagents used are commercially available or synthesized according to existing literature methods and purified before use.

Example 1: Preparation of Trans-1,2-Diaryl-3,3-Dibromocyclopropane III-b to III-d

Synthesis of trans-1,2-di-p-tolyl-3,3-dibromocyclopropane III-b

(9) ##STR00014##

(10) Under air, trans-1,2-di-p-tolyl ethylene (8.3 g, 40 mmol) and TEBAC (1.83 g, 8 mmol) were weighted and put into a 250 mL three-necked flask equipped with magnetic stirring, and 80 mL of CHBr.sub.3 was added. NaOH (88 g, 222 mmol) was added with 80 mL of water to prepare a saturated NaOH solution, and 80 mL of saturated NaOH aqueous solution was added dropwise to the three-necked flask at 0 C., followed by stirring continuously for 20 min at 0 C. and stirring at room temperature for 5 h. The reaction was quenched by the addition of water, a liquid was separated, and an aqueous phase was extracted with dichloromethane (100 mL3). An organic phase was washed before being dried with anhydrous Na.sub.2SO.sub.4. The dried organic phase was filtered, and a filtrate was concentrated by rotary evaporation, and the obtained crude product was separated by silica gel column chromatography (PE was used as an eluent) to obtain the product III-b (16.0 g, 95% yield), which was a faint yellow solid with a melting point of 55.1-56.2 C.

(11) .sup.1H NMR (400 MHZ, CDCl.sub.3) 7.26-7.24 (m, 4H), 7.20-7.18 (m, 4H), 3.18 (s, 2H), 2.36 (s, 6H).

(12) .sup.13C NMR (101 MHz, CDCl.sub.3) 137.67, 133.15, 129.26, 128.88, 39.86, 37.67, 21.37.

(13) The following compounds (III-c to III-d) were synthesized in the same method as III-b.

(14) trans-1,2-di-tert-butylphenyl-3,3-dibromocyclopropane III-c:

(15) ##STR00015##

(16) a faint yellow solid with a yield of 86% and a melting point of 119.1-120.5 C.

(17) .sup.1H NMR (400 MHZ, CDCl.sub.3) 7.43-7.39 (m, 4H), 7.31-7.28 (m, 4H), 3.19 (s, 2H), 1.34 (s, 18H).

(18) .sup.13C NMR (101 MHz, CDCl.sub.3) 150.87, 133.17, 128.68, 125.47, 39.98, 37.60, 34.76, 31.48.

(19) trans-1,2-bis (3,5-di-tert-butylphenyl)-3,3-dibromocyclopropane III-d:

(20) ##STR00016##

(21) a faint yellow solid with a yield of 61% and a melting point of 140.9-142.2 C.

(22) .sup.1H NMR (400 MHZ, CDCl.sub.3) 7.43-7.39 (m, 2H), 7.23-7.20 (m, 4H), 3.26 (s, 2H), 1.38 (s, 36H).

(23) .sup.13C NMR (101 MHz, CDCl.sub.3) 150.94, 135.43, 123.37, 121.76, 40.84, 37.91, 35.04, 31.64.

Example 2: Preparation of 1,2-Trans-Diaryl-3-Bromocyclopropane IV-a to IV-d

Synthesis of 1,2-trans-diphenyl-3-bromocyclopropane IV-a

(24) ##STR00017##

(25) under argon protection, LiBr (96 mg, 1.1 mmol), 1 mL of Et.sub.2O, and 1 mL of THF were added to a 10 mL dried Schlenk tube equipped with magnetic stirring. The system was cooled to 0 C. in an ice-water bath, and a solution of BuLi in n-hexane (440 L, 2.5 M, 1.1 mmol) was added slowly and dropwise. The system was then cooled to 100 C. using a liquid nitrogen-ethanol bath, and a solution of III-a (352 mg, 1 mmol) in THF (5 mL) was added dropwise using a syringe pump over approximately 1 h. The reaction system was quenched with methanol after being stirred at low temperature for 1 h. Water was added, and extraction was performed three times (10 mL3) with PE. Drying was performed with anhydrous MgSO.sub.4, and filtration was performed. A filtrate was concentrated by rotary evaporation, and the obtained crude product was separated by silica gel column chromatography (PE was used as an eluent) to obtain the product IV-a, which was a white solid (197 mg, 72% yield) with a melting point of 82.8-84.4 C.

(26) .sup.1H NMR (400 MHZ, CDCl.sub.3) 7.42-7.26 (m, 8H), 7.24-7.20 (m, 2H), 3.55 (dd, J=7.9, 4.4 Hz, 1H), 2.78 (dd, J=7.0, 4.4 Hz, 1H), 2.71-2.67 (m, 1H).

(27) .sup.13C NMR (101 MHZ, CDCl.sub.3) 139.63, 136.64, 129.29, 128.85, 128.27, 127.22, 126.96, 126.44, 32.48, 32.14, 30.63.

(28) The following compounds were synthesized in the same method as IV-a.

1,2-Trans-Di-p-Tolyl-3-Bromocyclopropane IV-b

(29) ##STR00018##

(30) a white solid with a yield of 55% and a melting point of 74.1-75.2 C.

(31) .sup.1H NMR (400 MHZ, CDCl.sub.3) 7.25-7.21 (m, 2H), 7.19-7.13 (m, 4H), 7.12-7.08 (m, 2H), 3.49 (dd, J=7.9, 4.3 Hz, 1H), 2.71 (dd, J=6.9, 4.3 Hz, 1H), 2.64-2.59 (m, 1H), 2.36 (s, 3H), 2.34 (s, 3H).

(32) .sup.13C NMR (101 MHz, CDCl.sub.3) 139.71, 136.75, 136.65, 136.51, 135.29, 133.65, 129.45, 129.10, 128.96, 126.29, 125.76, 32.12, 31.69, 30.98, 30.80, 21.29, 21.17.

1,2-Trans-Di-p-Tert-Butylphenyl-3-Bromocyclopropane IV-c

(33) ##STR00019##

(34) a yellow oily compound with a yield of 57%.

(35) .sup.1H NMR (400 MHZ, CDCl.sub.3) 7.37-7.33 (m, 4H), 7.28-7.23 (m, 2H), 7.14-7.09 (m, 2H), 3.48 (dd, J=7.9, 4.4 Hz, 1H), 2.71 (dd, J=6.9, 4.4 Hz, 1H), 2.63-2.56 (m, 1H), 1.32 (s, 9H), 1.30 (s, 9H).

(36) .sup.13C NMR (101 MHz, CDCl.sub.3) 149.84, 149.79, 136.76, 133.69, 128.87, 126.10, 125.68, 125.11, 34.60, 34.58, 32.33, 31.64, 31.52, 31.49, 31.40, 30.91, 27.05.

1,2-Trans-Bis (3,5-Di-Tert-Butylphenyl)-3-Bromocyclopropane IV-d

(37) ##STR00020##

(38) a yellow oily compound with a yield of 70%.

(39) .sup.1H NMR (400 MHZ, CDCl.sub.3) 7.36-7.33 (m, 2H), 7.21-7.18 (m, 2H), 7.08-7.05 (m, 2H), 3.56 (dd, J=7.8, 4.5 Hz, 1H), 2.78-2.69 (m, 2H), 1.36 (s, 18H), 1.34 (s, 18H).

(40) .sup.13C NMR (101 MHZ, CDCl.sub.3) 151.29, 150.38, 138.94, 135.81, 123.63, 121.16, 120.94, 120.67, 35.06, 34.98, 33.60, 32.23, 31.68, 31.65, 31.60, 31.33.

Example 3: Preparation of 2,3-Diarylcyclopropylphosphine Borane Adducts II-a to II-f

(41) Cyclopropane skeleton monophosphine ligands I-a to I-f are susceptible to oxidation, and borane adducts II-a to II-f thereof are in a stable form.

Synthesis of 2,3-Trans-Diphenylcyclopropyl Di-Tert-Butylphosphine Borane Adduct II-a

(42) ##STR00021##

(43) a reactant IV-a (300 mg, 1 mmol) was weighed and put into a 50 mL Schlenk flask equipped with magnetic stirring, and dissolved with anhydrous THF under argon atmosphere. A solution of BuLi in n-hexane (0.5 mL, 2.5 M, 1.2 mmol) was added dropwise at 100 C., and stirring was performed at this temperature for 1 h. Redistilled PBu.sub.2Cl (361 mg, 2 mmol) was added, and the reaction system was naturally warmed to room temperature and stirred for 4 h. After the reaction was monitored by TLC, the temperature was controlled in an ice-water bath (0 C.), a borane-THF solution (4 mL, 1.0 M, 4 mmol) was added to the system, after which the system was restored to room temperature and stirred for 12 h. The temperature was controlled in the ice-water bath, and the reaction system was quenched with water. An aqueous phase was extracted with EA (10 mL3), and the combined organic phases were dried with anhydrous MgSO.sub.4 and filtered. A filtrate was concentrated by rotary evaporation, and the obtained crude product was separated by silica gel column chromatography (eluent: PE/EA=100:1) to obtain the target product II-a (229 mg, 65% yield), which was a white solid with a melting point of 115-117 C.

(44) .sup.1H NMR (400 MHZ, CDCl.sub.3) 7.45-7.40 (m, 2H), 7.36-7.30 (m, 2H), 7.29-7.19 (m, 6H), 3.25-3.16 (m, 1H), 2.85-2.77 (m, 1H), 1.68-1.61 (m, 1H), 1.19 (d, J=12.3 Hz, 9H), 1.14 (d, J=12.7 Hz, 9H).

(45) .sup.13C NMR (101 MHZ, CDCl.sub.3) 140.45, 135.41, 135.39, 130.50, 128.92, 127.64, 127.08, 126.66, 125.84, 34.17, 34.12, 34.06, 33.78, 32.79, 32.52, 28.47, 28.45, 27.94, 27.93, 26.62, 22.25, 21.88.

(46) .sup.31P NMR (162 MHZ, CDCl.sub.3) 47.68, 47.16.

(47) .sup.11B NMR (128 MHZ, CDCl.sub.3) 42.81.

(48) HRMS (ESI) calcd for [M+Na, C.sub.23H34BNaP].sup.+: 375.2389, found: 375.2388.

(49) The following compounds were synthesized in the same method as II-a.

2,3-Trans-Di-p-Tolylphenylcyclopropyl Di-Tert-Butylphosphine Borane Adduct II-b

(50) ##STR00022##

(51) a white solid with a yield of 80% and a melting point of 174-176 C.

(52) .sup.1H NMR (400 MHZ, CDCl.sub.3) 7.33-7.29 (m, 2H), 7.17-7.12 (m, 4H), 7.10-7.06 (m, 2H), 3.20-3.11 (m, 1H), 2.79-2.71 (m, 1H), 2.34 (s, 3H), 2.31 (s, 3H), 1.61-1.56 (m, 1H), 1.20 (d, J=12.3 Hz, 9H), 1.15 (d, J=12.7 Hz, 9H).

(53) .sup.13C NMR (101 MHZ, CDCl.sub.3) 137.43, 136.47, 136.10, 132.36, 132.33, 130.30, 129.54, 128.29, 125.69, 33.99, 33.70, 32.74, 32.46, 28.51, 28.41, 27.97, 27.87, 26.37, 26.17, 21.25, 21.14.

(54) .sup.31P NMR (162 MHZ, CDCl.sub.3) 47.27, 46.82.

(55) .sup.11B NMR (128 MHz, CDCl.sub.3) 42.87.

(56) HRMS (ESI) calcd for [M+Na, C.sub.25H38BNaP].sup.+: 403.2702, found: 403.2701.

2,3-Trans-Di-p-Tert-Butylphenyl Cyclopropyl Di-Tert-Butylphosphine Borane Adduct II-c

(57) ##STR00023##

(58) a white solid with a yield of 48% and a melting point of 200-202 C.

(59) .sup.1H NMR (400 MHZ, CDCl.sub.3) 7.35-7.30 (m, 4H), 7.27-7.25 (m, 2H), 7.17-7.12 (m, 2H), 3.21-3.11 (m, 1H), 2.77-2.67 (m, 1H), 1.64-1.57 (m, 1H), 1.30 (s, 9H), 1.28 (s, 9H), 1.20 (d, J=12.2 Hz, 9H), 1.11 (d, J=12.7 Hz, 9H).

(60) .sup.13C NMR (101 MHZ, CDCl.sub.3) 149.81, 149.36, 137.39, 132.54, 132.51, 130.01, 125.67, 125.49, 124.44, 34.52, 34.50, 33.98, 33.78, 33.73, 33.69, 32.70, 32.42, 31.48, 31.46, 28.41, 28.39, 27.99, 27.97.

(61) .sup.31P NMR (162 MHZ, CDCl.sub.3) 47.43, 47.15.

(62) .sup.11B NMR (128 MHz, CDCl.sub.3) 43.20.

(63) HRMS (ESI) calcd for [M+Na, C.sub.31H50BNaP].sup.+: 487.3641, found: 487.3640.

2,3-Trans-Bis (3,5-Di-Tert-Butylphenyl) Cyclopropyldi-Tert-Butylphosphine Borane Adduct II-d

(64) ##STR00024##

(65) a white solid with a yield of 79% and a melting point of 195-197 C.

(66) .sup.1H NMR (400 MHZ, CDCl.sub.3) 7.26-7.24 (m, 4H), 7.10-7.07 (m, 2H), 3.32-3.24 (m, 1H), 2.93-2.83 (m, 1H), 1.56-1.50 (m, 1H), 1.33 (s, 36H), 1.21 (d, J=12.1 Hz, 9H), 1.09 (d, J=12.7 Hz, 9H).

(67) .sup.13C NMR (101 MHz, CDCl.sub.3) 151.06, 149.67, 139.35, 134.46, 134.43, 124.97, 120.74, 120.51, 120.49, 35.01, 34.94, 34.01, 33.72, 33.55, 33.50, 32.83, 32.56, 31.66, 31.66, 31.60, 28.55, 28.53, 28.00, 27.99, 26.99, 22.05, 21.68.

(68) .sup.31P NMR (162 MHZ, CDCl.sub.3) 47.68.

(69) .sup.11B NMR (128 MHz, CDCl.sub.3) 42.52.

(70) HRMS (ESI) calcd for [M+Na, C.sub.39H66BNaP].sup.+: 599.4893, found: 599.4895.

2,3-Trans-Diphenylcyclopropyldicyclohexylphosphine Borane Adduct II-e

(71) ##STR00025##

(72) a white solid with a yield of 80% and a melting point of 82-84 C.

(73) .sup.1H NMR (400 MHZ, CDCl.sub.3) 7.42-7.36 (m, 2H), 7.36-7.27 (m, 4H), 7.25-7.20 (m, 4H), 3.27-3.16 (m, 1H), 2.91-2.81 (m, 1H), 1.92-1.61 (m, 11H), 1.53-1.44 (m, 1H), 1.39-1.06 (m, 11H).

(74) .sup.13C NMR (101 MHz, CDCl.sub.3) 140.31, 135.60, 129.84, 128.65, 127.87, 127.05, 126.49, 126.11, 99.96, 34.62, 34.28, 33.05, 32.73, 32.09, 29.68, 27.29, 27.19, 27.07, 27.00, 26.91, 26.81, 26.77, 26.24, 25.95, 21.96, 21.53.

(75) .sub.31P NMR (162 MHZ, CDCl.sub.3) 29.52, 29.12.

(76) .sup.11B NMR (128 MHz, CDCl.sub.3) 43.40.

(77) HRMS (ESI) calcd for [M+Na, C.sub.27H38BNaP].sup.+: 427.2702, found: 427.2698.

Example 4: Preparation of 2,3-Diphenylcyclopropyl Diphenylphosphine I-f

(78) A cyclopropane skeleton monophosphine ligand I-f is in a stable form.

Synthesis of 2,3-Trans-Diphenylcyclopropyl Di-Tert-Butylphosphine I-f

(79) ##STR00026##

(80) a reactant IV-a (273 mg, 1 mmol) was weighed and put into a 50 mL Schlenk flask equipped with magnetic stirring, and dissolved with anhydrous THF under argon atmosphere. A solution of BuLi in n-hexane (0.5 mL, 2.5 M, 2.5 mmol) was added dropwise at 100 C., and stirring was performed at a low temperature for 1 h. Redistilled PPh.sub.2Cl (441 mg, 2 mmol) was added before the reaction system was naturally warmed up to room temperature and stirred for 4 h. The temperature of the reaction system was controlled in an ice-water bath, and the reaction system was quenched by adding water dropwise. An aqueous phase was extracted with EA (10 mL3), the combined organic phases were dried with anhydrous MgSO.sub.4 and filtered. A filtrate was concentrated by rotary evaporation, and the obtained crude product was purified by silica gel column chromatography (eluent: PE/EA=100:1). The target product I-f (303 mg, 80% yield) was obtained, which was a white solid with a melting point of 82-84 C.

(81) .sup.1H NMR (400 MHZ, CDCl.sub.3) 7.41-7.35 (m, 2H), 7.33-7.14 (m, 18H), 2.97-2.82 (m, 2H), 2.12-2.03 (m, 1H).

(82) .sup.13C NMR (101 MHZ, CDCl.sub.3) 141.29, 139.47, 139.37, 139.14, 139.04, 138.25, 138.19, 133.09, 132.90, 132.71, 132.53, 129.22, 129.19, 128.67, 128.57, 128.50, 128.44, 128.36, 128.29, 128.06, 126.65, 126.59, 126.37, 32.41, 32.35, 29.92, 29.84, 29.48, 29.35.

(83) .sup.31P NMR (162 MHZ, CDCl.sub.3) 16.18.

(84) HRMS (ESI) calcd for [M+H, C.sub.41H35P.sub.2].sup.+: 379.1616, found: 379.1615.

Example 5: Preparation of 1,2-Trans-Diphenyl-3-Bromo Gem-Methyl Cyclopropane V-a

(85) ##STR00027##

(86) IV-a (2.1 g, 6 mmol) was weighed and put into a 100 mL Schlenk flask. The gas in a system was replaced with an argon atmosphere, and anhydrous THF (30 mL) was added. The system was stirred at 78 C., and BuLi (2.4 mL, 2.5 M, 6 mmol) was added dropwise, with stirring at 78 C. for 10 min. Mel (3.4 g, 24 mmol) was added dropwise in the system, and the system was continued to be stirred at 78 C. for 30 min and then warmed to room temperature and stirred for 8 h. After the reaction was completed, saturated NH.sub.4Cl aqueous solution was added to quench the reaction. An aqueous phase was extracted with n-hexane (10 mL3), and the combined organic phase was dried with anhydrous Na.sub.2SO.sub.4, and filtered. A filtrate was concentrated by rotary evaporation, and the obtained crude product was separated by silica gel column chromatography (eluent: PE/EA=100:1). The target product V-a (1.3 g, 74% yield) was obtained, which was a colorless oily liquid.

(87) .sup.1H NMR (400 MHZ, CDCl.sub.3) 7.41-7.28 (m, 10H), 3.15 (d, J=7.7 Hz, 1H), 2.49 (d, J=7.7 Hz, 1H), 1.68 (s, 3H).

(88) A cyclopropane skeleton monophosphine ligand I-g is susceptible to oxidation and a borane adduct II-g thereof is in a stable form. The preparation of 2,3-trans-diphenyl-1-methylcyclopropane diphenylphosphine borane adduct II-g is as follows:

(89) ##STR00028##

(90) Mg crumbs (900 mg, 37.4 mmol) were weighed and put into a 50 mL three-necked round-bottomed flask, which was connected to a reflux condenser tube and a constant-pressure dropping funnel. The gas in the system was replaced with an argon atmosphere and the system was evacuated, and the system was heated and dried by a heating gun for 30 min and then filled with argon, and added with a small pellet of iodine after being returned to room temperature. Anhydrous THF (10 mL) was added, and a substrate V-a (2.15 g, 7.5 mmol) was transferred to the dropping funnel after being pre-dissolved in the anhydrous THF (5 mL). 5-10 drops of a substrate solution were added to the reaction system, and the system was heated by an air dryer to a slight boil to initiate the Grignard reaction. The rest of the substrate solution was added dropwise to keep the system in a slight boil state after the color of iodine has faded. The system was continued to be stirred at 50 C. for 30 min after the addition. Cul (1.71 g, 9 mmol) was weighed and put into another 100 mL Schlenk flask, and anhydrous THF (20 mL) was added. The prepared Grignard reagent was transferred to the Schlenk flask, and PPh.sub.2Cl (4.95 g, 22.5 mmol) was added, and heating was performed for 24 h at 50 C. Subsequently, a borane-THE solution (30 mmol, 1M in THF) was added dropwise at 0 C., and the reaction was resumed at room temperature for 8 h. After the reaction, the temperature was controlled by an ice-water bath, and the reaction was quenched by adding water dropwise. An aqueous phase was extracted with EA (20 mL3), and organic phases were combined, dried with anhydrous MgSO.sub.4, and filtered. A filtrate was concentrated by rotary evaporation, and the obtained crude product was separated by silica gel column chromatography (eluent: PE/EA=100:1) to obtain the target product II-g, which was a white solid (1.98 g, 65% yield) with a melting point of 139-141 C.

(91) .sup.1H NMR (400 MHZ, CDCl.sub.3) 7.57-7.47 (m, 4H), 7.46-7.35 (m, 6H), 7.34-7.25 (m, 5H), 7.11-6.95 (m, 5H), 3.47 (dd, J=14.4, 7.6 Hz, 1H), 2.92 (t, J=7.1 Hz, 1H), 1.25 (d, J=11.6 Hz, 3H).

(92) .sup.13C NMR (101 MHZ, CDCl.sub.3) 136.3, 135.0, 133.6, 133.5, 133.4, 130.8, 130.6, 129.7, 129.4, 128.5, 128.4, 128.3, 127.8, 127.1, 126.5, 36.3, 31.0, 19.3, 19.2.

(93) .sup.31P NMR (162 MHZ, CDCl.sub.3) 30.04.

(94) .sup.11B NMR (128 MHz, CDCl.sub.3) 38.29.

(95) HRMS (ESI) calcd for [M+Na, C.sub.28H28BNaP].sup.+: 429.1914, found: 429.1916.

Example 6: Preparation of 2,3-Trans-Diphenylcyclopropyl Di-Tert-Butylphosphine I-a

(96) ##STR00029##

(97) II-a (0.071 g, 0.2 mmol) and DABCO (0.067 g, 0.6 mmol) were weighed and put into a 25 mL Schlenk flask. The gas of the system was replaced with an argon atmosphere, and the system was stirred at 50 C. for 8 h after being added with anhydrous THF (4 mL). The obtained crude product was separated and purified by a silica gel column under anhydrous and anaerobic conditions to obtain the target product I-a, which was a colorless oily compound (0.064 g, 94% yield)

(98) .sup.1H NMR (400 MHZ, CDCl.sub.3) 7.33-7.24 (m, 6H), 7.23-7.14 (m, 4H), 2.63-2.55 (m, 1H), 2.55-2.47 (m, 1H), 1.79-1.71 (m, 1H), 1.16 (d, J=10.9 Hz, 9H), 0.95 (d, J=10.8 Hz, 9H).

(99) .sup.13C NMR (101 MHZ, CDCl.sub.3) 141.93, 139.73, 139.70, 128.64, 127.68, 126.06, 125.87, 125.71, 33.84, 33.81, 32.30, 32.28, 32.11, 32.09, 31.97, 31.87, 31.79, 30.45, 30.33, 30.22, 30.00, 29.92, 29.87, 29.79, 26.88, 26.80, 26.63, 26.53.

(100) .sup.31P NMR (162 MHz, CDCl.sub.3) 12.88.

(101) The following compounds were synthesized in the same method as I-a.

2,3-Trans-Di-p-Tolyl Cyclopropyl Di-Tert-Butylphosphine I-b

(102) ##STR00030##

(103) a colorless oily liquid with a yield of 95%.

(104) .sup.1H NMR (400 MHZ, CDCl.sub.3) 7.13-7.08 (m, 2H), 7.04-6.95 (m, 6H), 2.45 (dt, J=9.1, 6.3 Hz, 1H), 2.38-2.32 (m, 1H), 2.22 (s, 3H), 2.20 (s, 3H), 1.64-1.57 (m, 1H), 1.07 (d, J=10.8 Hz, 9H), 0.88 (d, J=10.8 Hz, 9H).

(105) .sup.13C NMR (101 MHZ, CDCl.sub.3) 138.97, 136.68, 136.65, 135.43, 135.18, 129.44, 129.38, 129.31, 129.26, 128.46, 128.35, 125.60, 33.38, 33.32, 32.29, 32.27, 32.11, 32.09, 31.40, 31.30, 31.20, 30.51, 30.35, 30.20, 30.07, 29.94, 29.81, 26.49, 26.26, 26.02, 21.13.

(106) .sup.31P NMR (162 MHZ, CDCl.sub.3) 13.01.

2,3-Trans-Di-p-Tert-Butylphenyl Cyclopropyl Di-Tert-Butylphosphine I-c

(107) ##STR00031##

(108) a colorless oily compound with a yield of 96%.

(109) .sup.1H NMR (400 MHZ, CDCl.sub.3) 7.24-7.18 (m, 4H), 7.16-7.12 (m, 2H), 7.06-7.01 (m, 2H), 2.53-2.44 (m, 1H), 2.38-2.32 (m, 1H), 1.69-1.61 (m, 1H), 1.22 (s, 9H), 1.20 (s, 9H), 1.10 (d, J=10.8 Hz, 9H), 0.88 (d, J=10.8 Hz, 9H).

(110) .sup.13C NMR (101 MHz, CDCl.sub.3) 148.72, 148.51, 138.91, 136.72, 136.69, 128.22, 125.58, 125.38, 124.67, 124.42, 34.49, 34.46, 33.35, 32.30, 32.28, 32.11, 31.61, 31.42, 31.26, 30.57, 30.42, 30.27, 30.03, 29.91, 29.79, 27.13, 26.01, 22.79, 14.32, 14.24.

(111) .sup.31P NMR (162 MHz, CDCl.sub.3) 13.01.

2,3-Trans-Bis (3,5-Di-Tert-Butylphenyl) Cyclopropyldi-Tert-Butylphosphine I-d

(112) ##STR00032##

(113) a colorless oily compound with a yield of 91%.

(114) .sup.1H NMR (400 MHZ, CDCl.sub.3) 7.19-7.06 (m, 4H), 7.05-6.94 (m, 2H), 2.58-2.44 (m, 1H), 2.44-2.29 (m, 1H), 1.75-1.61 (m, 1H), 1.35-1.21 (m, 36H), 1.16-1.07 (m, 9H), 0.88-0.74 (m, 9H).

(115) .sup.13C NMR (101 MHZ, CDCl.sub.3) 150.69, 149.51, 141.08, 139.23, 123.50, 123.32, 120.66, 120.61, 120.51, 119.87, 119.86, 119.40, 119.23, 35.03, 34.93, 34.02, 33.04, 32.28, 32.07, 31.82, 31.63, 30.64, 30.48, 30.34, 30.11, 29.99, 29.87, 25.05.

(116) .sup.31P NMR (162 MHZ, CDCl.sub.3) 14.58.

2,3-Trans-Di-Phenylcyclopropyldicyclohexylphosphine I-e

(117) ##STR00033##

(118) a colorless oily compound with a yield of 90%.

(119) .sup.1H NMR (400 MHz, CDCl.sub.3) 7.25-7.17 (m, 6H), 7.13-7.05 (m, 4H), 2.53-2.43 (m, 2H), 1.73-1.35 (m, 13H), 1.22-0.97 (m, 10H).

(120) .sup.13C NMR (101 MHz, CDCl.sub.3) 142.05, 139.33, 128.63, 127.69, 126.00, 33.99, 32.30, 31.01, 30.75, 30.17, 29.28, 27.45, 26.59, 26.43, 22.78, 14.30, 14.21.

(121) .sup.31P NMR (162 MHZ, CDCl.sub.3) 11.30.

2,3-Trans-Di-Phenyl-1-Gem-Methylcyclopropyl Diphenylphosphine I-g

(122) ##STR00034##

(123) a colorless oily compound with a yield of 96%.

(124) .sup.1H NMR (400 MHZ, CDCl.sub.3) 7.55-7.49 (m, 2H), 7.45-7.41 (m, 2H), 7.36-7.18 (m, 10H), 7.17-7.07 (m, 6H), 3.28 (dd, J=15.1, 6.7 Hz, 1H), 2.77 (dd, J=6.8, 3.7 Hz, 1H), 0.98 (d, J=2.8 Hz, 3H).

(125) .sup.13C NMR (101 MHZ, CDCl.sub.3) 138.44, 138.37, 137.40, 137.37, 137.29, 137.16, 136.60, 136.46, 133.92, 133.75, 133.57, 133.33, 129.42, 129.34, 129.25, 128.43, 128.23, 128.03, 127.96, 127.93, 127.86, 126.56, 126.51, 126.45, 36.12, 36.04, 35.94, 35.87, 34.20, 34.03, 33.86, 29.34, 29.22, 17.12, 16.98.

(126) .sup.31P NMR (162 MHZ, CDCl.sub.3) 7.44.

Example 7: Preparation of Palladium Complex VI-a

(127) ##STR00035##

(128) I-a (0.067 g, 0.2 mmol), (COD) Pd(CH.sub.2TMS) 2 (0.078 g, 0.2 mmol) and 2-(trimethylsilyl) ethyl 4-bromobenzoate (0.12 g, 0.4 mmol) were weighed and put into a 25 mL Schlenk flask, and the gas in a system was replaced with an argon atmosphere, and the system was stirred at room temperature for 12 h after being added with anhydrous n-hexane (4 mL). At the end of the reaction, the system was subjected to suction filtration and washed with n-hexane to obtain the target product VI-a (0.075 g, 50% yield), which was a yellow solid with a melting point of 108.1-110.2 C.

(129) .sup.1H NMR (400 MHZ, CDCl.sub.3) 8.24 (s, 2H), 7.76-7.27 (m, 7H), 7.18 (s, 5H), 4.36-4.26 (m, 2H), 2.79 (s, 1H), 1.75-1.40 (m, 11H), 1.11-1.02 (m, 2H), 0.77 (s, 9H), 0.05 (s, 9H).

(130) .sup.31P NMR (162 MHZ, CDCl.sub.3) 44.27, 40.59.

(131) Palladium complex VI-b:

(132) ##STR00036##

(133) a yellow solid with a yield of 65% and a melting point of 131.0-133.3 C.

(134) .sup.1H NMR (400 MHz, CDCl.sub.3) 8.01 (s, 2H), 7.59-7.32 (m, 5H), 7.17-6.81 (m, 5H), 4.32 (t, J=8.5 Hz, 2H), 2.69 (s, 1H), 2.45 (s, 3H), 2.32 (s, 3H), 1.87-1.35 (m, 10H), 1.28 (s, 1H), 1.08 (t, J=8.5 Hz, 2H), 0.81 (s, 9H), 0.06 (s, 9H).

(135) .sup.31P NMR (162 MHz, CDCl.sub.3) 46.01, 41.24.

(136) Palladium complex VI-c:

(137) ##STR00037##

(138) a yellow solid with a yield of 76% and a melting point of 158.1-160.0 C.

(139) .sup.1H NMR (400 MHZ, CDCl.sub.3) 8.64-7.86 (m, 2H), 7.81-7.36 (m, 5H), 7.24 (s, 5H), 4.33 (t, J=8.4 Hz, 2H), 2.93-2.60 (m, 1H), 1.71-1.49 (m, 9H), 1.45-1.26 (m, 20H), 1.13-1.05 (m, 2H), 0.77 (s, 9H), 0.06 (s, 9H).

(140) .sup.31P NMR (162 MHz, CDCl.sub.3) 43.65, 40.42, 39.03.

(141) Palladium complex VI-d:

(142) ##STR00038##

(143) a yellow solid with a yield of 80% and a melting point of 158.2-160.5 C.

(144) .sup.1H NMR (400 MHz, CDCl.sub.3) 7.89-7.28 (m, 7H), 7.21 (s, 1H), 7.03-6.79 (m, 2H), 4.34 (t, J=8.5 Hz, 2H), 1.62-1.40 (m, 27H), 1.38-1.20 (m, 28H), 1.11 (t, J=8.5 Hz, 4H), 0.09 (s, 9H).

(145) .sup.31P NMR (162 MHz, CDCl.sub.3) 56.36, 40.28.

(146) Palladium complex VI-e:

(147) ##STR00039##

(148) a faint yellow solid with a yield of 47% and a melting point of 140.1-142.5 C.

(149) .sup.1H NMR (400 MHZ, CDCl.sub.3) 8.21-7.86 (m, 2H), 7.85-6.82 (m, 12H), 4.37-4.23 (m, 2H), 3.12-2.77 (m, 1H), 2.24-1.59 (m, 10H), 1.32-0.84 (m, 16H), 0.07 (s, 9H).

(150) .sup.31P NMR (162 MHz, CDCl.sub.3) 29.21, 27.84, 22.23, 19.88.

(151) Palladium complex VI-f:

(152) ##STR00040##

(153) a faint yellow solid with a yield of 76% and a melting point of 126.2-128.4 C.

(154) .sup.1H NMR (400 MHZ, CDCl.sub.3) 7.49-7.07 (m, 20H), 7.03-6.83 (m, 4H), 4.34 (s, 2H), 2.93 (s, 1H), 1.33-1.29 (m, 1H), 1.14-1.05 (m, 2H), 0.92 (t, J=6.8 Hz, 1H), 0.09 (s, 9H).

(155) .sup.31P NMR (162 MHz, CDCl.sub.3) 23.00.

(156) Palladium complex VI-g:

(157) ##STR00041##

(158) a yellow solid with a yield of 75% and a melting point of 145.0-147.5 C.

(159) .sup.1H NMR (400 MHZ, CDCl.sub.3) 8.17-7.90 (m, 4H), 7.78-7.29 (m, 10H), 7.22-7.11 (m, 2H), 7.04-6.70 (m, 8H), 4.28 (t, J=8.3 Hz, 2H), 2.98 (t, J=7.6 Hz, 1H), 1.30 (s, 3H), 1.05 (t, J=8.2 Hz, 2H), 0.93 (s, 1H), 0.07 (s, 9H).

(160) .sup.31P NMR (162 MHZ, CDCl.sub.3) 30.82, 29.89.

Example 8: Preparation of Palladium Complex VI-h

(161) ##STR00042##

(162) I-a (0.067 g, 0.2 mmol), (COD) Pd(CH.sub.2TMS) 2 (0.078 g, 0.2 mmol) and bromobenzene (0.12 g, 0.4 mmol) were weighed and put into a 25 mL Schlenk flask, and the gas in the system was replaced with an argon atmosphere, and the system was stirred at room temperature for 12 h after being added with anhydrous n-hexane (4 mL). At the end of the reaction, the system was subjected to suction filtration and washed with n-hexane to obtain the target product VI-h (0.101 g, 83% yield), which was a yellow solid with a melting point of 161.1-162.5 C.

(163) .sup.1H NMR (400 MHZ, CDCl.sub.3) 8.17 (s, 2H), 7.69-7.60 (m, 2H), 7.40-7.34 (m, 1H), 7.17 (s, 7H), 6.82-6.66 (m, 3H), 2.75 (dt, J=10.7, 5.8 Hz, 1H), 1.64-1.41 (m, 10H), 1.26 (s, 1H), 0.93-0.69 (m, 9H).

(164) .sup.31P NMR (162 MHZ, CDCl.sub.3) 40.96, 37.30.

(165) TABLE-US-00001 TABLE 1 single-crystal test parameters for II-c Empirical formula C.sub.31H.sub.50BP Formula weight 464.49 Temperature/K. 113.15 Crystal system Triclinic Space group P-1 a/ 6.6990(2) b/ 16.1601(4) c/ 31.1766(9) / 86.949(2) / 89.408(2) / 89.936(2) Volume/.sup.3 3370.11(16) Z 4 .sub.calc g/cm.sup.3 0.915 /mm.sup.1 0.095 F(000) 1024.0 Crystal size/mm.sup.3 0.24 0.22 0.18 Radiation MoK ( = 0.71073) 2 range for data 3.538 to 52.742 collection/ Index ranges 8 h 8, 20 k 20, 38 l 38 Reflections collected 29767 Independent 13595 [R.sub.int = 0.0573, reflections R.sub.sigma = 0.0764] Data/restraints/ 13595/12/643 parameters Goodness-of-fit 1.024 on F.sup.2 Final R indexes R.sub.1 = 0.0876, [I >= 2 (I)] wR.sub.2 = 0.2339 Final R indexes R.sub.1 = 0.1195, [all data] wR.sub.2 = 0.2614 Largest diff. peak/ 0.89/0.33 hole/e .sup.3

(166) TABLE-US-00002 TABLE 2 single-crystal test parameters for palladium complex VI-h Empirical formula C.sub.29H.sub.36BPPd Formula weight 601.86 Temperature/K. 113.15 Crystal system Monoclinic Space group P2.sub.1/c a/ 9.7940(3) b/ 15.6650(4) c/ 17.6785(5) / 90 / 101.215(3) / 90 Volume/.sup.3 2660.50(13) Z 4 .sub.cal cg/cm.sup.3 1.503 /mm.sup.1 2.274 F(000) 1224.0 Crystal size/mm.sup.3 0.26 0.24 0.22 Radiation MoK ( = 0.71073) 2 range for data 4.698 to 59.15 collection/ Index ranges 13 h 13, 21 h 21, 24 l 24, Reflections collected 35498 Independent 7468 [R.sub.int = 0.0513, reflections R.sub.sigma = 0.0378] Data/restraints/ 7468/0/296 parameters Goodness-of-fit 1.042 on F.sup.2 Final R indexes R.sub.1 = 0.0330, [I >= 2 (I)] wR.sub.2 = 0.0730 Final R indexes R.sub.1 = 0.0450, [all data] wR.sub.2 = 0.0783 Largest diff. peak/ 0.79/1.07 hole/e .sup.3

Example 9: Palladium-Catalyzed CN Bond Coupling Reactions in the Presence of Different Solvents

(167) ##STR00043##

(168) In an argon-filled glove box, diphenylamine (169 mg, 1 mmol), bromobenzene (173 mg, 1.1 mmol), sodium tert-butanolate (125 mg, 1.3 mmol), and a solvent (2 mL) were added to a 25 mL Schlenk tube, to which, 0.0183 g of [(allyl) PdCl].sub.2 toluene solution (1 mg/g) and 0.0704 g of ligand II-a toluene solution (1 mg/g) were subsequently added, and stirring was performed for 24 h after the tube was plugged with a rubber stopper. At the end of the reaction, a reaction liquid was filtered through a dropper column, and a filtrate was concentrated by rotary evaporation and added with n-tridecane as an internal standard. The yield and turnover frequency were calculated using GC.

(169) TABLE-US-00003 TABLE 3 experimental results of palladium-catalyzed coupling reaction of bromobenzene with diphenylamine in the presence of different solvents Turnover Serial Temperature frequency Yield Turnover number Solvent ( C.) (%).sup.a (%).sup.a number 1 PhCF.sub.3 100 11 7 700 2 Benzene 80 16 11 1100 3 Toluene 110 >99 97 9700 4 O-xylene 110 >99 96 9600 5 DMF 110 30 19 1900 .sup.aTurnover frequency and yield were measured by GC.

Example 10: Palladium-Catalyzed Coupling of Bromobenzene with Diphenylamine in the Presence of Different Alkali

(170) ##STR00044##

(171) In an argon-filled glove box, diphenylamine (169 mg, 1 mmol), bromobenzene (173 mg, 1.1 mmol), alkali (1.3 mmol), and toluene (2 mL) were added to a 25 mL Schlenk tube, to which, 0.0183 g of [(allyl) PdCl].sub.2 toluene solution (1 mg/g) and 0.0704 g of ligand II-a toluene solution (1 mg/g) were subsequently added, and stirring was performed at 110 C. for 24 h after the tube was plugged with a rubber stopper. At the end of the reaction, a reaction liquid was filtered through a dropper column, and a filtrate was concentrated by rotary evaporation and added with n-tridecane as an internal standard. The yield and turnover frequency were calculated using GC.

(172) TABLE-US-00004 TABLE 4 experimental results of palladium-catalyzed coupling reaction of bromobenzene with diphenylamine in the presence of different alkali Turnover Serial frequency Turnover number Alkali (%).sup.a Yield (%).sup.a number 1 NaO.sup.tBu >99 98 9800 2 KO.sup.tBu 54 17 1700 3 LiO.sup.tBu 62 57 5700 5 NaOEt 9 7 700 6 KOTMS 25 24 2400 15 NaH >99 99 9900 .sup.aTurnover frequency and yield were measured by GC.

Example 11: Modulation of CN Bond Coupling Reaction by Cyclopropane Skeleton Monophosphine Ligand-Borane Adducts in the Presence of Different Palladium Catalysts

(173) ##STR00045##

(174) In an argon-filled glove box, diphenylamine (169 mg, 1 mmol), bromobenzene (173 mg, 1.1 mmol), sodium tert-butoxide (125 mg, 1.3 mmol), and toluene (2 mL) were added to a 25 mL Schlenk tube, to which, the prepared toluene solution (1 mg/g) of Pd and a toluene solution (1 mg/g) of ligand II were subsequently added, and stirring was performed at 110 C. for 24 h after the tube was plugged with a rubber stopper. At the end of the reaction, a reaction liquid was filtered through a dropper column, and a filtrate was concentrated by rotary evaporation and added with n-tridecane as an internal standard. The yield and turnover frequency were calculated using GC.

(175) TABLE-US-00005 TABLE 5 experimental results of cyclopropane skeleton monophosphine ligand- borane adducts modulating the coupling of bromobenzene with diphenylamine in the presence of different palladium catalysts Turnover Serial frequency Turnover number [Pd] x II (%).sup.a Yield (%).sup.a number 1 [(allyl)PdCl].sub.2 0.005 II-a >99 97 9700 2 [(allyl)PdCl].sub.2 0.0025 II-a 89 88 17600 3 Pd.sub.2(dba).sub.3CHCl.sub.3 0.0025 II-a 80 78 15600 4 Pd.sub.2(dba).sub.4 0.0025 II-a 81 80 16000 5 Pd(OAc).sub.2 0.005 II-a 82 81 16200 6 Pd(TFA).sub.2 0.005 II-a 74 74 14800 7 VI-a 0.005 II-a 93 93 18600 8.sup.b VI-a 0.005 II-a >99 97 19400 9.sup.b VI-b 0.005 II-b 96 95 19000 10.sup.b VI-c 0.005 II-c 91 90 18000 11.sup.b VI-d 0.005 II-d >99 97 19400 12.sup.b VI-e 0.005 II-e 91 90 18000 13.sup.b VI-f 0.005 II-f 48 45 9000 14.sup.b VI-g 0.005 II-g 55 51 10200 15.sup.b VI-h 0.005 II-a 85 80 16000 16.sup.bc VI-a 0.005 II-a 80 79 15800 17.sup.b VI-a 0.005 Non 59 58 11600 18.sup.b VI-a 0.002 II-a 45 40 20000 .sup.aTurnover frequency and yield were measured by GC. .sup.bII (2x mol %), 125 C. .sup.cII (1x mol %).

Example 12: Substrate Evaluation for Palladium-Catalyzed CN Bond Coupling Reaction

(176) ##STR00046##

(177) In an argon-filled glove box, secondary amine (1 mmol), a bromoaromatic compound (1.1 mmol), sodium tert-butoxide (125 mg, 1.3 mmol), and toluene (2 mL) were added to a 25 mL Schlenk tube, to which, a toluene solution of [(allyl) PdCl].sub.2 (1 mg/mL) and a toluene solution of ligand II-a (1 mg/mL) were added, and stirring was performed at 110 C. for 24 h after the tube was plugged with a rubber stopper. At the end of the reaction, the separation yield was calculated by column chromatography.

(178) TABLE-US-00006 TABLE 6 substrate range for palladium-catalyzed CN bond coupling reaction Comparative Serial [Pd] Yield Turnover documentary number Raw material Product structure (%) (%).sup.a number record 1 0.005.sup.c 97 19400 235.sup.[1] 2 0 0.005.sup.b 97 9700 3 0.005.sup.b 99 9900 90.sup.[2] 4 0.02.sup.cf 99 4950 86.sup.[3] 5 0.025.sup.be 90 1800 6 0.01.sup.be 91 4550 3680.sup.[4] 7 0 0.01.sup.be 99 4950 3680.sup.[4] 8 0.005.sup.ce 99 19800 4667.sup.[5] 9 0.01.sup.b 99 4950 3804.sup.[6] 10 0.01.sup.bd 89 4450 170.sup.[7] 11 0.01.sup.be 85 4250 172.sup.[7] 12 0 0.01.sup.b 95 4750 38.sup.[8] 13 0.05.sup.cf 99 1980 68.sup.[9] 14 0.1.sup.cf 80 800 36.sup.[10] 15 0.01.sup.be 98 4900 45.sup.[10] .sup.aseparation; .sup.b[(allyl)PdCl].sub.2 serves as a catalyst; .sup.cVi-a serves as a catalyst; .sup.d125 C.; .sup.e150 C., 12 h, o-xylene (2 mL); .sup.f180 C., 12 h, and o-xylene (2 mL). Bibliography: .sup.[1]Hajipour, A. R.; Dordahan, F.; Rafiee, F. Appl. Organometal. Chem. 2013, 27, 704. .sup.[2]Xue, Y.-Y.; Guo, P.-P.; Yip, H.; Li, Y.; Cao, Y. J. Mater. Chem. A. 2017, 5, 3780. .sup.[3]Steiner, A.; Williams, J. D.; Rincon, J. A.; Frutos, O. D.; Mateos, C. Eur. J. Org. Chem. 2019, 5807. .sup.[4]Yamamoto, T.; Nishiyama, M.; Koie, Y. Tetrahedron Lett. 1998, 39, 2367. .sup.[5]Silberg, J.; Schareina, T.; Kempa, R.; Wurst, K.; Buchmeiser, M. R. J. Organomet. Chem. 2001, 622, 6. .sup.[6]Heshmatpour, F.; Abazari, R. RSC Adv. 2014, 4, 55815. .sup.[7]Prashad, M.; Mak, X. Y.; Liu, Y.-G.; Repic, O. J. Org. Chem. 2003, 68, 1163. .sup.[8]Mao, J.-Y.; Zhang, J.-D.; Zhang, S.-G.; Walsh, P. J. Dalton Trans. 2018, 47, 8690. .sup.[9]Basolo, L.; Bernasconi, A.; Broggini, G.; Beccalli, E. M. ChemSusChem 2011, 4, 1637. .sup.[10]Shao, Q.-L.; Jiang, Z. J.; Su, W.-K. Tetrahedron Lett. 2018, 59, 2277.

Example 13: Palladium-Catalyzed CN Bond Coupling of Chlorobenzene with Diphenylamine

(179) ##STR00077##

(180) In an argon-filled glove box, diphenylamine (203 mg, 1.2 mmol), chlorobenzene (113 mg, 1 mmol), sodium tert-butanolate (125 mg, 1.3 mmol), and o-xylene (2 mL) were added to a 25 mL Schlenk tube, to which, 0.0183 g of [(allyl) PdCl].sub.2 o-xylene solution (1 mg/mL) and 0.0704 g of ligand II-a o-xylene solution (1 mg/mL) were subsequently added, and stirring was performed at 150 C. for 12 h after the tube was plugged with a rubber stopper. At the end of the reaction, a reaction liquid was filtered through a dropper column, and a filtrate was concentrated by rotary evaporation and added with n-tridecane as an internal standard. The yield and turnver number were 87% and 8700, respectively, calculated by GC.

(181) The above are only preferred embodiments of the present invention, and it is to be noted that, for those ordinary skilled in the art, several deformations and improvements may be made without departing from the conception of the present invention, all of which fall within the scope of protection of the present invention.