Strategic vinyl sulfone nucleophile β-substitution significantly impacts selectivity in Vinylogous Darzens and aza-Darzens reactions

Michael D. Delost; Jon T. Njardarson

doi:10.1021/acs.orglett.0c02448

Strategic vinyl sulfone nucleophile β-substitution significantly impacts selectivity in Vinylogous Darzens and aza-Darzens reactions

Michael D. Delost, Jon T. Njardarson

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

9 Scopus citations

Abstract

Vinylogous Darzens and aza-Darzens reactions employing a benzothiophene 1,1-dioxide nucleophile are reported. These new [2 + 1] annulation reactions, which proceed under mild reaction conditions, are γ-selective, affording trans-epoxides selectively and favoring trans-aziridines. The reactions are base-dependent, with KOtBu and Cs2CO3 being optimal for aldehyde and imine annulations, respectively. Comparison of the benzothiophene nucleophile to its acyclic counterpart reveals superior performance in the case of aldehydes, while the outcome varies depending on the sulfonamide imine used.

Original language	English (US)
Pages (from-to)	6917-6921
Number of pages	5
Journal	Organic Letters
Volume	22
Issue number	17
DOIs	https://doi.org/10.1021/acs.orglett.0c02448
State	Published - Sep 4 2020
Externally published	Yes

ASJC Scopus subject areas

Biochemistry
Physical and Theoretical Chemistry
Organic Chemistry

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10.1021/acs.orglett.0c02448

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abstract = "Vinylogous Darzens and aza-Darzens reactions employing a benzothiophene 1,1-dioxide nucleophile are reported. These new [2 + 1] annulation reactions, which proceed under mild reaction conditions, are γ-selective, affording trans-epoxides selectively and favoring trans-aziridines. The reactions are base-dependent, with KOtBu and Cs2CO3 being optimal for aldehyde and imine annulations, respectively. Comparison of the benzothiophene nucleophile to its acyclic counterpart reveals superior performance in the case of aldehydes, while the outcome varies depending on the sulfonamide imine used.",

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AU - Delost, Michael D.

AU - Njardarson, Jon T.

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Y1 - 2020/9/4

N2 - Vinylogous Darzens and aza-Darzens reactions employing a benzothiophene 1,1-dioxide nucleophile are reported. These new [2 + 1] annulation reactions, which proceed under mild reaction conditions, are γ-selective, affording trans-epoxides selectively and favoring trans-aziridines. The reactions are base-dependent, with KOtBu and Cs2CO3 being optimal for aldehyde and imine annulations, respectively. Comparison of the benzothiophene nucleophile to its acyclic counterpart reveals superior performance in the case of aldehydes, while the outcome varies depending on the sulfonamide imine used.

AB - Vinylogous Darzens and aza-Darzens reactions employing a benzothiophene 1,1-dioxide nucleophile are reported. These new [2 + 1] annulation reactions, which proceed under mild reaction conditions, are γ-selective, affording trans-epoxides selectively and favoring trans-aziridines. The reactions are base-dependent, with KOtBu and Cs2CO3 being optimal for aldehyde and imine annulations, respectively. Comparison of the benzothiophene nucleophile to its acyclic counterpart reveals superior performance in the case of aldehydes, while the outcome varies depending on the sulfonamide imine used.

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Strategic vinyl sulfone nucleophile β-substitution significantly impacts selectivity in Vinylogous Darzens and aza-Darzens reactions

Abstract

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CCDC 2000082: Experimental Crystal Structure Determination

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Strategic vinyl sulfone nucleophile β-substitution significantly impacts selectivity in Vinylogous Darzens and aza-Darzens reactions

Abstract

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CCDC 2000082: Experimental Crystal Structure Determination

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