Open AccessCatalyst-Controlled Regiodivergence in Rearrangements of Indole-Based Onium Ylides
Author(s) -
Vaishnavi Nair,
Volga Kojasoy,
Croix Laconsay,
Wang-Yeuk Kong,
Dean J. Tantillo,
Uttam K. Tambar
Publication year - 2021
Publication title -
journal of the american chemical society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 7.115
H-Index - 612
eISSN - 1520-5126
pISSN - 0002-7863
DOI - 10.1021/jacs.1c00283
Subject(s) - chemistry , oxonium ion , ylide , indole test , catalysis , rhodium , density functional theory , diazo , combinatorial chemistry , onium , stereochemistry , computational chemistry , photochemistry , medicinal chemistry , organic chemistry , ion
We have developed catalyst-controlled regiodivergent rearrangements of onium-ylides derived from indole substrates. Oxonium ylides formed in situ from substituted indoles selectively undergo [2,3]- and [1,2]-rearrangements in the presence of a rhodium and a copper catalyst, respectively. The combined experimental and density functional theory (DFT) computational studies indicate divergent mechanistic pathways involving a metal-free ylide in the rhodium catalyzed reaction favoring [2,3]-rearrangement, and a metal-coordinated ion-pair in the copper catalyzed [1,2]-rearrangement that recombines in the solvent-cage. The application of our methodology was demonstrated in the first total synthesis of the indole alkaloid (±)-sorazolon B, which enabled the stereochemical reassignment of the natural product. Further functional group transformations of the rearrangement products to generate valuable synthetic intermediates were also demonstrated.