Synthesis of Alkyl- Or Aryl-Substituted Hetelocycles: Nickel Complex Catalyzed Coupling Reaction of Heterocyclic Sulfides and Thiols With Grignard Reagents

Abstract

Heterocyclic sulfides and thiols react with Grignard reagents in the presence of NiCl2(Ph2PCH2CH2CH2PPh2) to afford the cross-coupling products in high yields. The reaction of 2,2′-dipyridyl disulfide with 3-phenylpropylmagnesium bromide is also described.

Advances in Transition Metal (Pd,Ni,Fe)-Catalyzed Cross-Coupling Reactions Using Alkyl-organometallics as Reaction Partners

“…Later, the scope was expanded to include allyl sulfides and heterocyclic sulfides 350. Ni(dppp)Cl 2 (3 mol%) was the catalyst of choice for the coupling of various alkylMgBr with heterocyclic sulfides.…”

“…Based on this observation, a mechanism for the reaction with disulfides was proposed (Figure 92). 350…”

C–S Bond Activation

“…Organosulfur compounds, such as aryl sulfides, sulfoxides, and sulfones, have been also known to serve as electrophilic counterparts in cross-coupling reactions. In 1979, Takei [22,23] and Wenkert [24] independently reported pioneering works in this field by means of a nickel catalyst and organomagnesium reagents (Scheme 10).…”

Cross-Coupling Reactions Catalyzed by Iron Group Metals and <i>N</i>-Heterocyclic Carbenes via Nonconventional Reaction Mechanisms

“…Despite a long history starting with independent publications by Wenkert 58 and Takei 59 in 1979, organosulfur compounds 60 have received far less attention as electrophilic substrates in cross coupling chemistry than other substrates, such as halides, sulfonates, and phosphates. The underuse of organosulfur compounds is partly due to their malodorous smell 61 and the perception that they are a lesser substitute for other electrophiles.…”