In:
Angewandte Chemie, Wiley, Vol. 132, No. 45 ( 2020-11-02), p. 20295-20303
Abstract:
Catalyst‐free addition of ketone enolate to non‐activated multiple C−C bonds involves non‐complementary reaction partners and typically requires super‐basic conditions. On the other hand, highly aggregated or solvated enolates are not reactive enough to undergo direct addition to alkenes or alkynes. Herein, we report a new anionic cascade reaction for one‐step assembly of intriguing molecular scaffolds possessing contiguous six‐, five‐, and four‐membered rings, representing a formal [2+2] enol–allene cycloaddition. Reaction proceeds under very mild conditions and with excellent diastereoselectivity. Deeper mechanistic and computational studies revealed unusually slow proton transfer phenomenon in cyclic ketone intermediate and explained peculiar stereochemical outcome.
Type of Medium:
Online Resource
ISSN:
0044-8249
,
1521-3757
DOI:
10.1002/ange.v132.45
DOI:
10.1002/ange.202008317
Language:
English
Publisher:
Wiley
Publication Date:
2020
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