Merging Photoexcited Nitroarenes with Lewis Acid Catalysis for the Anti-Markovnikov Oxidation of Alkenes

Joshua M. Paolillo; Mahmoud R. Saleh; Ethan W. Junk; Marvin Parasram

doi:10.1021/acs.orglett.5c00389

Merging Photoexcited Nitroarenes with Lewis Acid Catalysis for the Anti-Markovnikov Oxidation of Alkenes

Joshua M. Paolillo, Mahmoud R. Saleh, Ethan W. Junk, Marvin Parasram

Chemistry

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

Abstract

Herein we describe the oxidation of alkenes to carbonyls and acetonides via the interplay of photoexcited nitroarenes and Lewis acid catalysis. A wide range of alkenes were oxidized to aldehyde and ketone products with anti-Markovnikov selectivity and to acetonides when acetone was employed as a co-solvent. Mechanistic studies support that Lewis acid coordination to the 1,3,2-dioxazolidine intermediate results in a 1,2-shift to generate carbonyl derivatives and a nucleophilic substitution pathway for the formation of acetonides.

Original language	English (US)
Pages (from-to)	2011-2015
Number of pages	5
Journal	Organic Letters
Volume	27
Issue number	8
DOIs	https://doi.org/10.1021/acs.orglett.5c00389
State	Published - Feb 28 2025

ASJC Scopus subject areas

Biochemistry
Physical and Theoretical Chemistry
Organic Chemistry

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title = "Merging Photoexcited Nitroarenes with Lewis Acid Catalysis for the Anti-Markovnikov Oxidation of Alkenes",

abstract = "Herein we describe the oxidation of alkenes to carbonyls and acetonides via the interplay of photoexcited nitroarenes and Lewis acid catalysis. A wide range of alkenes were oxidized to aldehyde and ketone products with anti-Markovnikov selectivity and to acetonides when acetone was employed as a co-solvent. Mechanistic studies support that Lewis acid coordination to the 1,3,2-dioxazolidine intermediate results in a 1,2-shift to generate carbonyl derivatives and a nucleophilic substitution pathway for the formation of acetonides.",

author = "Paolillo, {Joshua M.} and Saleh, {Mahmoud R.} and Junk, {Ethan W.} and Marvin Parasram",

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AU - Saleh, Mahmoud R.

AU - Junk, Ethan W.

AU - Parasram, Marvin

PY - 2025/2/28

Y1 - 2025/2/28

N2 - Herein we describe the oxidation of alkenes to carbonyls and acetonides via the interplay of photoexcited nitroarenes and Lewis acid catalysis. A wide range of alkenes were oxidized to aldehyde and ketone products with anti-Markovnikov selectivity and to acetonides when acetone was employed as a co-solvent. Mechanistic studies support that Lewis acid coordination to the 1,3,2-dioxazolidine intermediate results in a 1,2-shift to generate carbonyl derivatives and a nucleophilic substitution pathway for the formation of acetonides.

AB - Herein we describe the oxidation of alkenes to carbonyls and acetonides via the interplay of photoexcited nitroarenes and Lewis acid catalysis. A wide range of alkenes were oxidized to aldehyde and ketone products with anti-Markovnikov selectivity and to acetonides when acetone was employed as a co-solvent. Mechanistic studies support that Lewis acid coordination to the 1,3,2-dioxazolidine intermediate results in a 1,2-shift to generate carbonyl derivatives and a nucleophilic substitution pathway for the formation of acetonides.

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SN - 1523-7060

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JO - Organic Letters

JF - Organic Letters

IS - 8

ER -

Merging Photoexcited Nitroarenes with Lewis Acid Catalysis for the Anti-Markovnikov Oxidation of Alkenes

Abstract

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