Dearomative Mislow–Braverman–Evans Rearrangement of Aryl Sulfoxides DOI Creative Commons
Xinping Zhang, Jiliang Li, Madeline E. Rotella

et al.

JACS Au, Journal Year: 2025, Volume and Issue: 5(2), P. 998 - 1006

Published: Feb. 5, 2025

The Mislow–Braverman–Evans rearrangement, the reversible [2,3]-sigmatropic rearrangement of allylic sulfoxides to sulfenate esters, finds widespread applications in organic synthesis and medicinal chemistry. However, products this powerful strategy have primarily been limited derivatives alcohols. In contrast, access structurally similar benzylic alcohols has not yet established. Described herein is an unprecedented dearomative aryl afford A variety heteroaryl as well α-naphthyl could be tolerated, a diverse range primary, secondary, tertiary possessing either alkyl or substituents can prepared by our protocol with broad functional group tolerance. patented bioactive molecule using key step exclusive diastereoselectivity, highlighting its potential utility synthesis. Key success transformation tautomerization shift reactive alkene exocyclic position enabled deprotonation C–H bond, setting stage for subsequent rearrangement. Density theory (DFT) calculations reveal that protonation α-carbon sulfoxide stereocontrolling step, generating intermediate undergoes full reaction profile outlined, showing nature each which causes observed erosion enantiopurity.

Language: Английский

Dearomative Mislow–Braverman–Evans Rearrangement of Aryl Sulfoxides DOI Creative Commons
Xinping Zhang, Jiliang Li, Madeline E. Rotella

et al.

JACS Au, Journal Year: 2025, Volume and Issue: 5(2), P. 998 - 1006

Published: Feb. 5, 2025

The Mislow–Braverman–Evans rearrangement, the reversible [2,3]-sigmatropic rearrangement of allylic sulfoxides to sulfenate esters, finds widespread applications in organic synthesis and medicinal chemistry. However, products this powerful strategy have primarily been limited derivatives alcohols. In contrast, access structurally similar benzylic alcohols has not yet established. Described herein is an unprecedented dearomative aryl afford A variety heteroaryl as well α-naphthyl could be tolerated, a diverse range primary, secondary, tertiary possessing either alkyl or substituents can prepared by our protocol with broad functional group tolerance. patented bioactive molecule using key step exclusive diastereoselectivity, highlighting its potential utility synthesis. Key success transformation tautomerization shift reactive alkene exocyclic position enabled deprotonation C–H bond, setting stage for subsequent rearrangement. Density theory (DFT) calculations reveal that protonation α-carbon sulfoxide stereocontrolling step, generating intermediate undergoes full reaction profile outlined, showing nature each which causes observed erosion enantiopurity.

Language: Английский

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