Synfacts 2005(1): 0136-0136  
DOI: 10.1055/s-2005-872187
Metal-Catalyzed Asymmetric Synthesis and Stereoselective Reactions
© Georg Thieme Verlag Stuttgart · New York

anti-1,2-Diols via a Ni-Catalyzed Reductive Coupling

Contributor(s): Mark Lautens, Josephine Yuen
T. Luanphaisarnnont, C. O. Ndubaku, T. F. Jamison*
Massachusetts Institute of Technology, USA
Further Information

Publication History

Publication Date:
21 September 2005 (online)


anti-1,2-Diols were prepared using a nickel-catalyzed reductive coupling of alkynes to α-oxyaldehydes. Both the MOM- and PMB-protected alcohols gave the anti-1,2-diol products despite the fact that these protecting groups typically display a preference for syn-1,2-diols. The observed sense of induction was explained by the absence of a chelating metal in the reaction allowing a ‘dipolar’ transition state to predominate. Larger substituents on the side of the alkyne where C-C bond formation occurs improves the diastereoselectivity but gives poorer yields. Heteroatom substituents on the alkyne are also tolerated.