@article{5f992a7da3244be1ae0bfd0aed9a2b0b,
title = "Catalyst-Controlled Regiodivergence in Rearrangements of Indole-Based Onium Ylides",
abstract = "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.",
author = "Nair, {Vaishnavi N.} and Volga Kojasoy and Laconsay, {Croix J.} and Kong, {Wang Yeuk} and Tantillo, {Dean J.} and Tambar, {Uttam K.}",
note = "Funding Information: Financial support was provided to U.K.T by W. W. Caruth, Jr. Endowed Scholarship, Welch Foundation (I-1748), National Institutes of Health (R01GM102604), American Chemical Society Petroleum Research Fund (59177-ND1), Teva Pharmaceuticals Marc A. Goshko Memorial Grant (60011-TEV), and Sloan Research Fellowship. Financial support was provided to V.N.N by Sarah and Frank McKnight Fund Graduate Fellowship. Support from the National Science Foundation (CHE-1856416 and XSEDE via CHE-030089) to D.J.T. is gratefully acknowledged. We acknowledge Dr. Vincent Lynch (Manager of the X-ray Diffraction Lab at UT Austin) for the X-ray structural analysis and Dr. Hamid Baniasadi (Director of the UT Southwestern Metabolomics Core Facility) for the high resolution mass spectrometry. We also thank our diverse group of lab members for creating an environment that supports our scientific endeavors. Publisher Copyright: {\textcopyright} 2021 American Chemical Society.",
year = "2021",
month = jun,
day = "23",
doi = "10.1021/jacs.1c00283",
language = "English (US)",
volume = "143",
pages = "9016--9025",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "24",
}