American Chemical Society
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1,3-Steric Induction in Intermolecular Radical Reactions Mediated by a Co2(CO)6−Metal Core

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journal contribution
posted on 2010-08-23, 00:00 authored by Gagik G. Melikyan, Ryan Spencer, Aaron Rowe
Diastereoselectivity of propargyl coupling reactions can be controlled by using the bulkiness of a γ-substituent as a stereochemical tool. This 1,3-steric induction was observed with γ-t-Bu and γ-Me3Si groups, both favoring a d,l-configuration of the head-to-head coupling products, 3,4-disubstituted 1,5-alkadiynes (d,l- 95−100%). X-ray crystallography analysis suggests that the most favorable orientation of converging propargyl radicals is the one in which the bulky γ-substituents are positioned anti to each other. Overall, the synthetic strategy of employing a Me3Si auxiliary group involves five steps and affords, with 28−33% overall yields, pure d,l-3,4-diaryl-1,5-hexadiynes, otherwise hardly accessible.