The invention discloses a method for preparation of alkylated, fluoro alkylated, chloro alkylated and fluorochloro alkylated compounds by a heterogeneous Co-catalysed alkylation or fluoro, chloro and fluorochloro alkylation with alkyl halides, fluoro alkyl halides, chloro alkyl halides or fluorochloro alkyl halides respectively.

The invention discloses a method for preparation of alkylated, fluoro alkylated, chloro alkylated and fluorochloro alkylated compounds by a heterogeneous Co-catalysed alkylation or fluoro, chloro and fluorochloro alkylation with alkyl halides, fluoro alkyl halides, chloro alkyl halides or fluorochloro alkyl halides respectively.

A metal cyclopentadienyl complex has the formula: ##STR00001##
wherein m?0; M is a Group I, II or III main group metal, alkali or transition metal; C.sub.5H.sub.4 represents a Cp ring where two hydrogens are substituted by M and R(F).sub.m; R(F).sub.m is connected to any one of the carbon atoms of the Cp and selected from a hydrocarbyl, fluorohydrocarbyl, silyl group [SiR.sub.3], or amino group [NR.sup.1R.sup.2]. The metal cyclopentadienyl complexes include Li(C.sub.5H.sub.4-2-C.sub.5H.sub.11) (CAS No: 2413046-23-6), K(C.sub.5H.sub.4-2-C.sub.5H.sub.11), Na(C.sub.5H.sub.4-2-C.sub.5H.sub.11), K(C.sub.5H.sub.4-1-FC.sub.4H.sub.10), K(C.sub.5H.sub.4-1,1,1-3FC.sub.4H.sub.6), Li(C.sub.5H.sub.4-2-C.sub.4H.sub.9), or In(C.sub.5H.sub.4-2-C.sub.5H.sub.11) (CAS No.: 2364634-67-1). A mono-substituted cyclopentadiene has the formula: ##STR00002##
wherein m?0; C.sub.5H.sub.5 represents the Cp ring where one hydrogen is substituted R(F).sub.m; R(F).sub.m is connected to any one of the carbon atoms of the Cp and selected from a hydrocarbyl, fluorohydrocarbyl, silyl group [SiR.sub.3], or amino group [NR.sup.1R.sup.2]. The mono-substituted cyclopentadienes include C.sub.5H.sub.5-1-FC.sub.4H.sub.10, C.sub.5H.sub.5-2-C.sub.5H.sub.11, C.sub.5H.sub.5-2-C.sub.4H.sub.9, or C.sub.5H.sub.5-1,1,1-3FC.sub.4H.sub.6.

A metal cyclopentadienyl complex has the formula: ##STR00001##
wherein m?0; M is a Group I, II or III main group metal, alkali or transition metal; C.sub.5H.sub.4 represents a Cp ring where two hydrogens are substituted by M and R(F).sub.m; R(F).sub.m is connected to any one of the carbon atoms of the Cp and selected from a hydrocarbyl, fluorohydrocarbyl, silyl group [SiR.sub.3], or amino group [NR.sup.1R.sup.2]. The metal cyclopentadienyl complexes include Li(C.sub.5H.sub.4-2-C.sub.5H.sub.11) (CAS No: 2413046-23-6), K(C.sub.5H.sub.4-2-C.sub.5H.sub.11), Na(C.sub.5H.sub.4-2-C.sub.5H.sub.11), K(C.sub.5H.sub.4-1-FC.sub.4H.sub.10), K(C.sub.5H.sub.4-1,1,1-3FC.sub.4H.sub.6), Li(C.sub.5H.sub.4-2-C.sub.4H.sub.9), or In(C.sub.5H.sub.4-2-C.sub.5H.sub.11) (CAS No.: 2364634-67-1). A mono-substituted cyclopentadiene has the formula: ##STR00002##
wherein m?0; C.sub.5H.sub.5 represents the Cp ring where one hydrogen is substituted R(F).sub.m; R(F).sub.m is connected to any one of the carbon atoms of the Cp and selected from a hydrocarbyl, fluorohydrocarbyl, silyl group [SiR.sub.3], or amino group [NR.sup.1R.sup.2]. The mono-substituted cyclopentadienes include C.sub.5H.sub.5-1-FC.sub.4H.sub.10, C.sub.5H.sub.5-2-C.sub.5H.sub.11, C.sub.5H.sub.5-2-C.sub.4H.sub.9, or C.sub.5H.sub.5-1,1,1-3FC.sub.4H.sub.6.

A metal cyclopentadienyl complex has the formula: ##STR00001##
wherein m?0; M is a Group I, II or III main group metal, alkali or transition metal; C.sub.5H.sub.4 represents a Cp ring where two hydrogens are substituted by M and R(F).sub.m; R(F).sub.m is connected to any one of the carbon atoms of the Cp and selected from a hydrocarbyl, fluorohydrocarbyl, silyl group [SiR.sub.3], or amino group [NR.sup.1R.sup.2]. The metal cyclopentadienyl complexes include Li(C.sub.5H.sub.4-2-C.sub.5H.sub.11) (CAS No: 2413046-23-6), K(C.sub.5H.sub.4-2-C.sub.5H.sub.11), Na(C.sub.5H.sub.4-2-C.sub.5H.sub.11), K(C.sub.5H.sub.4-1-FC.sub.4H.sub.10), K(C.sub.5H.sub.4-1,1,1-3FC.sub.4H.sub.6), Li(C.sub.5H.sub.4-2-C.sub.4H.sub.9), or In(C.sub.5H.sub.4-2-C.sub.5H.sub.11) (CAS No.: 2364634-67-1). A mono-substituted cyclopentadiene has the formula: ##STR00002##
wherein m?0; C.sub.5H.sub.5 represents the Cp ring where one hydrogen is substituted R(F).sub.m; R(F).sub.m is connected to any one of the carbon atoms of the Cp and selected from a hydrocarbyl, fluorohydrocarbyl, silyl group [SiR.sub.3], or amino group [NR.sup.1R.sup.2]. The mono-substituted cyclopentadienes include C.sub.5H.sub.5-1-FC.sub.4H.sub.10, C.sub.5H.sub.5-2-C.sub.5H.sub.11, C.sub.5H.sub.5-2-C.sub.4H.sub.9, or C.sub.5H.sub.5-1,1,1-3FC.sub.4H.sub.6.

The present application provides, among other things, compounds and methods for metathesis reactions. In some embodiments, the present disclosure provides methods for preparing alkenyl halide with regioselectivity and/or stereoselectivity. In some embodiments, the present disclosure provides methods for preparing alkenyl halide with regioselectivity and Z-selectivity. In some embodiments, the present disclosure provides methods for preparing alkenyl halide with regioselectivity and E-selectivity. In some embodiments, provided technologies are particularly useful for preparing alkenyl fluorides. In some embodiments, a provided compound useful for metathesis reactions has the structure of formula II-a. In some embodiments, a provided compound useful for metathesis reactions has the structure of formula II-b.

The present application provides, among other things, compounds and methods for metathesis reactions. In some embodiments, the present disclosure provides methods for preparing alkenyl halide with regioselectivity and/or stereoselectivity. In some embodiments, the present disclosure provides methods for preparing alkenyl halide with regioselectivity and Z-selectivity. In some embodiments, the present disclosure provides methods for preparing alkenyl halide with regioselectivity and E-selectivity. In some embodiments, provided technologies are particularly useful for preparing alkenyl fluorides. In some embodiments, a provided compound useful for metathesis reactions has the structure of formula II-a. In some embodiments, a provided compound useful for metathesis reactions has the structure of formula II-b.

The present invention relates to a novel a process for the preparation of 9-dichloromethylene-1,2,3,4-tetrahydro-1,4-methano-naphthalen-5-ylamine which process comprises a) reacting cyclopentadiene in the presence of a radical initiator and CXCl3, wherein X is chloro or bromo, to a compound of formula I1, or aa) reacting cyclopentadiene with CXCl3, wherein X is chloro, in the presence of a metal catalyst to a compound of formula I1, wherein X is chloro, b) reacting the compound of formula I1 with a base in the presence of an appropriate solvent to the compound of formula III, c) and converting the compound of formula III in the presence of 1,2-dehydro-6-nitrobenzene to the compound of formula IV, and d) hydrogenating the compound of formula IV in the presence of a metal catalyst.

The present invention relates to a novel a process for the preparation of 9-dichloromethylene-1,2,3,4-tetrahydro-1,4-methano-naphthalen-5-ylamine which process comprises a) reacting cyclopentadiene in the presence of a radical initiator and CXCl3, wherein X is chloro or bromo, to a compound of formula I1, or aa) reacting cyclopentadiene with CXCl3, wherein X is chloro, in the presence of a metal catalyst to a compound of formula I1, wherein X is chloro, b) reacting the compound of formula I1 with a base in the presence of an appropriate solvent to the compound of formula III, c) and converting the compound of formula III in the presence of 1,2-dehydro-6-nitrobenzene to the compound of formula IV, and d) hydrogenating the compound of formula IV in the presence of a metal catalyst.

The present invention relates to a novel a process for the preparation of 9-dichloromethylene-1,2,3,4-tetrahydro-1,4-methano-naphthalen-5-ylamine which process comprises a) reacting cyclopentadiene in the presence of a radical initiator and CXCl3, wherein X is chloro or bromo, to a compound of formula I1, or aa) reacting cyclopentadiene with CXCl3, wherein X is chloro, in the presence of a metal catalyst to a compound of formula I1, wherein X is chloro, b) reacting the compound of formula I1 with a base in the presence of an appropriate solvent to the compound of formula III, c) and converting the compound of formula III in the presence of 1,2-dehydro-6-nitrobenzene to the compound of formula IV, and d) hydrogenating the compound of formula IV in the presence of a metal catalyst.