Dataset Information

A formal intermolecular [4 + 1] cycloaddition reaction of 3-chlorooxindole and o-quinone methides: a facile synthesis of spirocyclic oxindole scaffolds.

ABSTRACT: Herein, we developed an efficient and straightforward method for the rapid synthesis of spirocyclic oxindole scaffolds via the [4 + 1] cyclization reaction of 3-chlorooxindole with o-quinone methides (o-QMs), which were generated under mild conditions. The products could be obtained in excellent yields with numerous types of 3-chlorooxindole. This methodology features mild reaction conditions, high atom-economy and broad substrate scope.

SUBMITTER: Lin C

PROVIDER: S-EPMC9033455 | biostudies-literature | 2021 May

REPOSITORIES: biostudies-literature

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A formal intermolecular [4 + 1] cycloaddition reaction of 3-chlorooxindole and o-quinone methides: a facile synthesis of spirocyclic oxindole scaffolds.

Lin Chao C Xing Qi Q Xie Honglei H

RSC advances 20210524 30

Herein, we developed an efficient and straightforward method for the rapid synthesis of spirocyclic oxindole scaffolds via the [4 + 1] cyclization reaction of 3-chlorooxindole with o-quinone methides (o-QMs), which were generated under mild conditions. The products could be obtained in excellent yields with numerous types of 3-chlorooxindole. This methodology features mild reaction conditions, high atom-economy and broad substrate scope. ...[more]

PMID: 35480909

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Project description:CONSPECTUS: An ortho-quinone methide (o-QM) is a highly reactive chemical motif harnessed by nature for a variety of purposes. Given its extraordinary reactivity and biological importance, it is surprising how few applications within organic synthesis exist. We speculate that their widespread use has been slowed by the complications that surround the preparation of their precursors, the harsh generation methods, and the omission of this stratagem from computer databases due to its ephemeral nature. About a decade ago, we discovered a mild anionic triggering procedure to generate transitory o-QMs at low temperature from readily available salicylaldehydes, particularly OBoc derivatives. This novel reaction cascade included both the o-QM formation and the subsequent consumption reaction. The overall transformation was initiated by the addition of the organometallic reagent, usually a Grignard reagent, which resulted in the formation of a benzyloxy alkoxide. Boc migration from the neighboring phenol produced a magnesium phenoxide that we supposed underwent β-elimination of the transferred Boc residue to form an o-QM for immediate further reactions. Moreover, the cascade proved controllable through careful manipulation of metallic and temperature levers so that it could be paused, stopped, or restarted at various intermediates and stages. This new level of domestication enabled us to deploy o-QMs for the first time in a range of applications including diastereocontrolled reactions. This sequence ultimately could be performed in either multipot or single pot processes. The subsequent reaction of the fleeting o-QM intermediates included the 1,4-conjugate additions that led to unbranched or branched ortho-alkyl substituted phenols and Diels-Alder reactions that provided 4-unsubstituted or 4-substituted benzopyrans and chroman ketals. The latter cycloadducts were obtained for the first time with outstanding diastereocontrol. In addition, the steric effects of the newly created stereocenters in subsequent reactions of chroman ketals and acetals were studied and proved predictable. Through the use of a chiral auxiliary, Diels-Alder products were deployed in numerous enantioselective reactions including several complex natural products syntheses. In this Account, we summarize our efforts, which we hope have contributed to the synthetic renaissance for this venerable species.

Dataset Information

A formal intermolecular [4 + 1] cycloaddition reaction of 3-chlorooxindole and o-quinone methides: a facile synthesis of spirocyclic oxindole scaffolds.

Publications

A formal intermolecular [4 + 1] cycloaddition reaction of 3-chlorooxindole and <i>o</i>-quinone methides: a facile synthesis of spirocyclic oxindole scaffolds.

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