Organoactinide-, organolanthanide-, and organogroup-4-mediated hydrothiolation of terminal alkynes with aliphatic, aromatic and benzylic thiols

Abstract

An efficient and highly Markovnikov selective organoactinide-, organolanthanide-, and organozirconium-catalyzed addition of aryl, benzyl, and aliphatic thiols to terminal alkynes is described. The corresponding vinyl sulfides are produced with little or no side-products.

What is claimed is: 
     
         1 . A vinyl sulfide of formula 
       
         
           
           
               
               
           
         
         prepared by the steps comprising 
         1) reacting a thiol of formula
   R″—SH
 
 
         with a terminal alkyne of formula II
   ≡—′
 
 
         in the presence of a catalyst selected from the group consisting of; 
         a) CGCM 1 R 1   2 , wherein M 1  is selected from an actinide metal and Zr(IV), and R 1  is selected from NMe 2 , NEt 2  and Me; 
         b) CGCM 2 R 2 , wherein M 2  is lanthanide metal and R 2  is N(TMS) 2 ; 
         c) Cp* 2  M 1 R 3   2 , wherein R 3  is selected from NMe 2 , NEt 2 , Me and CH 2 TMS; 
         d) Cp* 2 M 2 R 4 , wherein R 4  is selected from N(TMS) 2  and CH(TMS) 2 ; 
         e) Me 2 SiCp″M 3 R 5   2 , wherein M 3  is an actinide metal, and R 5  is selected from CH 2 TMS and Bn; 
         M 1 [R 4 ] 3 ; 
         g) Cp* M 4 R 6 , wherein M 4  is a Group 4 metal and R 6  is selected from Bn and Cl 2 NMe 2 ; and M 4 (R 3 ) 4 ; and 
         h) M 4 (R 3 ) 4 , 
         wherein R′ and R″ are independently selected from the group consisting of alkyl, aryl, heteroaryl, cycloalkyl, arylalkyl, heteroarylalkyl and cycloalkylalkyl; and 
         2) isolating the vinyl sulfide. 
       
     
     
         2 . A vinyl sulfide of  claim 1  wherein the catalyst is selected from Cp *   2 SmN(TMS) 2 , Me 2 SiCp″ 2 Th[CH 2 (TMS)] 2 . CGCZrMe 2 , Cp *   2 YCH(TMS) 2 , Me 2 SiCp″ 2 UBn 2 , Cp *   2 ZrMe 2 , CGCSmN(TMS) 2 , CGCU(NMe 2 ) 2 , Cp*ZrBn 3 , La[N(TMS) 2 ] 3 , CGCTh(NMe 2 ) 2 , Zr[NMe 2 ] 4 , Nd[N(TMS) 2 ] 3 , U(NEt 2 ) 4 , Cp*ZrCl 2 NMe 2 , Lu[CH(TMS) 2 ] 3 , Cp *   2 U(NMe 2 ) 2 , Y[N(TMS) 2 ] 3 , Cp *   2 Th(CH 2 TMS) 2 , Cp *   2 LaCH(TMS) 2 , Cp *   2 U(CH 2 TMS) 2 , Cp *   2 SmCH(TMS) 2 , and Cp *   2 LuCH(TMS) 2 . 
     
     
         3 . A vinyl sulfide according to  claim 1  selected from the group consisting of
 a) hex-1-en-2-yl(pentyl)sulfane; 
 b) cyclohexyl(hex-1-en-2-yl)sulfane; 
 c) hex-1-en-2-yl(4-methylbenzyl)sulfane; 
 d) pentyl(1-phenylvinyl)sulfane; 
 e) (1-(cyclohex-1-en-1-yl)vinyl)(pentyl)sulfane 
 f) (1-cyclohexylvinyl)(pentyl)sulfane; 
 g) (1-cyclohexylvinyl)(4-methylbenzyl)sulfane; 
 h) ethyl(hex-1-en-2-yl)sulfane; 
 i) hex- 1-en-2-yl(2,2,2-trifluoroethyl)sulfane; 
 j) benzyl(hex-1-en-2-yl)sulfane; 
 k) (3-cyclohexylprop-1-en-2-yl)(pentyl)sulfane; 
 l) pentyl(3-phenylprop-1-en-2-yl)sulfane; 
 m) 3-(1-(pentylthio)vinyl)pyridine; and 
 n) 2-(pentylthio)prop-2-en-1-amine.