Journal ArticleDOI
Visible‐Light‐Initiated Manganese Catalysis for C−H Alkylation of Heteroarenes: Applications and Mechanistic Studies
Philippe Nuhant,Martins S. Oderinde,Julien Genovino,Antoine Juneau,Yohann Gagné,Christophe Allais,Gary Chinigo,Chulho Choi,Neal W. Sach,Louise Bernier,Yvette M. Fobian,Mark W. Bundesmann,Bhagyashree Khunte,Mathieu Frenette,Olugbeminiyi O. Fadeyi +14 more
TLDR
A visible-light-driven Minisci protocol that employs an inexpensive earth-abundant metal catalyst, decacarbonyldimanganese Mn2 (CO)10 , to generateAlkyl radicals from alkyl iodides has been developed and is demonstrated on the late-stage functionalization of complex nitrogen-containing drugs.Abstract:
A visible-light-driven Minisci protocol that employs an inexpensive earth-abundant metal catalyst, decacarbonyldimanganese Mn2 (CO)10 , to generate alkyl radicals from alkyl iodides has been developed. This Minisci protocol is compatible with a wide array of sensitive functional groups, including oxetanes, sugar moieties, azetidines, tert-butyl carbamates (Boc-group), cyclobutanes, and spirocycles. The robustness of this protocol is demonstrated on the late-stage functionalization of complex nitrogen-containing drugs. Photophysical and DFT studies indicate a light-initiated chain reaction mechanism propagated by . Mn(CO)5 . The rate-limiting step is the iodine abstraction from an alkyl iodide by . Mn(CO)5 .read more
Citations
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Journal ArticleDOI
Metallaphotoredox: The Merger of Photoredox and Transition Metal Catalysis.
Amy Y. Chan,Ian B. Perry,Noah B. Bissonnette,Benito F. Buksh,Grant A. Edwards,Lucas I. Frye,Olivia L. Garry,Marissa N. Lavagnino,Beryl X. Li,Yufan Liang,Edna Mao,Agustin Millet,James V. Oakley,Nicholas L. Reed,Holt A. Sakai,Ciaran P. Seath,David W. C. MacMillan +16 more
TL;DR: The merger of photoredox catalysis with transition metal catalysis has become a mainstay in synthetic methodology over the past decade as discussed by the authors, which has combined the unparalleled capacity of transition metal catalysts for bond formation with the broad utility of photoinduced electron and energy-transfer processes.
Journal ArticleDOI
Recent Advances in Minisci-Type Reactions.
TL;DR: A review of the remarkably large body of literature that has appeared on this topic over the last decade in an attempt to provide guidance to the synthetic chemist, as well as a perspective on both the challenges that have been overcome and those that still remain.
Journal ArticleDOI
Visible Light-Induced Transition Metal Catalysis.
TL;DR: In this paper, a transition metal complex serves a double duty by harvesting photon energy and then enabling bond forming/breaking events mostly via a single catalytic cycle, thus contrasting the established dual photocatalysis in which an exogenous photosensitizer is employed.
Journal ArticleDOI
Transition Metal-Catalyzed Organic Reactions under Visible Light: Recent Developments and Future Perspectives
TL;DR: The development of transition metal (TM) catalysis for organic synthesis under visible light without recourse to typical photoredox catalysts has become a rapidly growing area of research and has b...
Journal ArticleDOI
Generation of Alkyl Radicals: From the Tyranny of Tin to the Photon Democracy.
Stefano Crespi,Maurizio Fagnoni +1 more
TL;DR: This review summarizes the main alternative approaches for the generation of unstabilized alkyl radicals, using photons as traceless promoters, thus allowing a new era of photon democracy.
References
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Alcohols as alkylating agents in heteroarene C-H functionalization
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