In:
Angewandte Chemie, Wiley, Vol. 134, No. 51 ( 2022-12-19)
Abstract:
The first copper‐catalyzed regiodivergent cyanoboration of internal allenes with B 2 pin 2 (bis(pinacolato)diboron) and NCTS ( N‐ cyano ‐N ‐phenyl‐ p ‐toluenesulfonamide) derivatives is reported. The β,γ‐ and α,β‐cyanoborylated products were synthesized with high regio‐ and stereo‐selectivity. Computational studies revealed that nucleophilic addition of allylcopper or related intermediates on cyanation reagent is the regio‐ and stereo‐determining step, while transmetalation with B 2 pin 2 is the rate‐determining step. The nucleophilic addition step proceeds via inner‐sphere mechanism in the Cu I /P( o ‐tol) 3 and Cu I /Xantphos (P( o ‐tol) 3 =tris( o ‐methylphenyl)phosphine, Xantphos=4,5‐bis(diphenylphosphino)‐9,9‐dimethylxanthene) catalytic systems and via outer‐sphere mechanism in the Cu II /Xantphos catalytic system, respectively.
Type of Medium:
Online Resource
ISSN:
0044-8249
,
1521-3757
DOI:
10.1002/ange.v134.51
DOI:
10.1002/ange.202210338
Language:
English
Publisher:
Wiley
Publication Date:
2022
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