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. 2005 Jul 7;7(14):2937-40.
doi: 10.1021/ol050881k.

anti-1,2-Diols via Ni-catalyzed reductive coupling of alkynes and alpha-oxyaldehydes

Torsak Luanphaisarnnont  1 , Chudi O Ndubaku, Timothy F Jamison
Affiliations

anti-1,2-Diols via Ni-catalyzed reductive coupling of alkynes and alpha-oxyaldehydes

Torsak Luanphaisarnnont et al. Org Lett. .

Abstract

[reaction: see text] Ni-catalyzed reductive coupling of aryl alkynes (1) and enantiomerically enriched alpha-oxyaldehydes (2) afford differentiated anti-1,2-diols (3) with high diastereoselectivity and regioselectivity, despite the fact that the methoxymethyl (MOM) and para-methoxybenzyl (PMB) protective groups typically favor syn-1,2-diol formation in carbonyl addition reactions of this family of aldehydes.

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Figures

Figure 1
Figure 1
Models for stereoselective nucleophilic additions to α-oxyaldehydes. (A) The cyclic “Cram-chelate” model predicts syn-1,2-diols. (B) The “dipolar” model predicts anti-1,2-diols.
Scheme 1
Scheme 1
Catalytic Asymmetric Reductive Coupling of Alkynes and Aldehydes
Scheme 2
Scheme 2
Assignment of the Relative Configuration of 3a
Figure 2
Figure 2
Schematic representation of divergent pathways leading to syn- and anti-1,2-diols.
See this image and copyright information in PMC

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