A radical-initiated fragmentary rearrangement cascade of ene-ynamides to [1,2]-annulated indoles via site-selective cyclization

Sifan Li; Yu Wang; Zibo Wu; weilang shi; Yibo lei; Paul Davies; Wei Shu

doi:10.1021/acs.orglett.1c02519

A radical-initiated fragmentary rearrangement cascade of ene-ynamides to [1,2]-annulated indoles via site-selective cyclization

Sifan Li, Yu Wang, Zibo Wu, weilang shi, Yibo lei, Paul Davies, Wei Shu

Chemistry

Research output: Contribution to journal › Letter › peer-review

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Abstract

Straightforward access to [1,2]-annulated indoles, key substructures in natural products, is highly desirable yet challenging. Herein, a radical triggered fragmentary cyclization cascade reaction of ene-ynamides is presented, providing a rapid access into [1,2]-annulated indoles by an intermolecular radical addition, intramolecular cyclization, desulfonylative aryl migration, and site-selective C(sp2)-N cyclization sequence. DFT calculations support oxidation of N-centered radical species to cations prior to the C–N bond formation, followed by an unusual aza-Nazarov cyclization.

Original language	English
Pages (from-to)	7209-7214
Journal	Organic Letters
Volume	23
Issue number	18
Early online date	28 Aug 2021
DOIs	https://doi.org/10.1021/acs.orglett.1c02519
Publication status	E-pub ahead of print - 28 Aug 2021

ASJC Scopus subject areas

Biochemistry
Physical and Theoretical Chemistry
Organic Chemistry

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10.1021/acs.orglett.1c02519

LiS2021radical
This document is the Accepted Manuscript version of a Published Work that appeared in final form in Organic Letters, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see: https://doi.org/10.1021/acs.orglett.1c02519
Accepted author manuscript, 1.29 MBLicence: None: All rights reserved

1 Article

Modular synthesis of α-Arylated carboxylic acids, esters and amides via photocatalyzed triple C−F bond cleavage of methyltrifluorides
Li, S., Davies, P. & Shu, W., 12 May 2022, In: Chemical Science. 2022, 22, p. 6636-6641
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title = "A radical-initiated fragmentary rearrangement cascade of ene-ynamides to [1,2]-annulated indoles via site-selective cyclization",

abstract = "Straightforward access to [1,2]-annulated indoles, key substructures in natural products, is highly desirable yet challenging. Herein, a radical triggered fragmentary cyclization cascade reaction of ene-ynamides is presented, providing a rapid access into [1,2]-annulated indoles by an intermolecular radical addition, intramolecular cyclization, desulfonylative aryl migration, and site-selective C(sp2)-N cyclization sequence. DFT calculations support oxidation of N-centered radical species to cations prior to the C–N bond formation, followed by an unusual aza-Nazarov cyclization.",

author = "Sifan Li and Yu Wang and Zibo Wu and weilang shi and Yibo lei and Paul Davies and Wei Shu",

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T1 - A radical-initiated fragmentary rearrangement cascade of ene-ynamides to [1,2]-annulated indoles via site-selective cyclization

AU - Li, Sifan

AU - Wang, Yu

AU - Wu, Zibo

AU - shi, weilang

AU - lei, Yibo

AU - Davies, Paul

AU - Shu, Wei

PY - 2021/8/28

Y1 - 2021/8/28

N2 - Straightforward access to [1,2]-annulated indoles, key substructures in natural products, is highly desirable yet challenging. Herein, a radical triggered fragmentary cyclization cascade reaction of ene-ynamides is presented, providing a rapid access into [1,2]-annulated indoles by an intermolecular radical addition, intramolecular cyclization, desulfonylative aryl migration, and site-selective C(sp2)-N cyclization sequence. DFT calculations support oxidation of N-centered radical species to cations prior to the C–N bond formation, followed by an unusual aza-Nazarov cyclization.

AB - Straightforward access to [1,2]-annulated indoles, key substructures in natural products, is highly desirable yet challenging. Herein, a radical triggered fragmentary cyclization cascade reaction of ene-ynamides is presented, providing a rapid access into [1,2]-annulated indoles by an intermolecular radical addition, intramolecular cyclization, desulfonylative aryl migration, and site-selective C(sp2)-N cyclization sequence. DFT calculations support oxidation of N-centered radical species to cations prior to the C–N bond formation, followed by an unusual aza-Nazarov cyclization.

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U2 - 10.1021/acs.orglett.1c02519

DO - 10.1021/acs.orglett.1c02519

M3 - Letter

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VL - 23

SP - 7209

EP - 7214

JO - Organic Letters

JF - Organic Letters

IS - 18

ER -

A radical-initiated fragmentary rearrangement cascade of ene-ynamides to [1,2]-annulated indoles via site-selective cyclization

Abstract

ASJC Scopus subject areas

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Research output

Modular synthesis of α-Arylated carboxylic acids, esters and amides via photocatalyzed triple C−F bond cleavage of methyltrifluorides

Cite this