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. 2023 Feb 2;14(9):2461-2466.
doi: 10.1039/d2sc05768a. eCollection 2023 Mar 1.

Intramolecular trapping of spiro radicals to produce unusual cyclization products from usual migration substrates

Jingming Zhang  1 , Chengkou Liu  1 , Yaqi Qiao  1 , Minghui Wei  1 , Wenjing Guan  1 , Ziren Mao  1 , Hong Qin  1 , Zheng Fang  1 , Kai Guo  1   2
Affiliations

Intramolecular trapping of spiro radicals to produce unusual cyclization products from usual migration substrates

Jingming Zhang et al. Chem Sci. .

Abstract

A conceptually new methodology to give unusual cyclization products from usual migration substrates was disclosed. The highly complex and structurally important and valuable spirocyclic compounds were produced through radical addition, intramolecular cyclization and ring opening instead of usual migration to the di-functionalization products of olefins. Furthermore, a plausible mechanism was proposed based on a series of mechanistic studies including radical trapping, radical clock, verification experiments of intermediates, isotope labeling and KIE experiments.

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Conflict of interest statement

There are no conflicts to declare.

Figures

Scheme 1
Scheme 1. Design of radical-promoted addition/cyclization/ring-opening of 1,4-enynes. (a) Nevado's work: aryl migration/desulfonylation/H abstraction or cyclization; (b) Zhu's work: radical addition/distal functional group migration; (c) This work: radical addition/intramolecular cyclization/ring-opening.
Scheme 2
Scheme 2. Radical-trapping and clock experiments. (a) Radical-trapping experiments; (b) clock experiments. BHT: butylated hydroxytoluene.
Scheme 3
Scheme 3. Verification experiments of intermediates. (a) The monitoring of 42 and the desired product 3; (b) verification experiment of intermediate 43.
Scheme 4
Scheme 4. Isotope labeling and KIE experiments. (a) Isotope labeling experiments; (b) KIE experiments.
Scheme 5
Scheme 5. Proposed mechanism for this intramolecular trapping of the spiro radicals to produce unusual cyclization products from the usual migration substrates.
See this image and copyright information in PMC

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