Ti-catalyzed ring-opening oxidative amination of methylenecyclopropanes with diazenes.

Chemical Science
Evan P BeaumierIan A Tonks

Abstract

The ring-opening oxidative amination of methylenecyclopropanes (MCPs) with diazenes catalyzed by py3TiCl2(NR) complexes is reported. This reaction selectively generates branched α-methylene imines as opposed to linear α,β-unsaturated imines, which are difficult to access via other methods. Products can be isolated as the imine or hydrolyzed to the corresponding ketone in good yields. Mechanistic investigation via density functional theory suggests that the regioselectivity of these products results from a Curtin-Hammett kinetic scenario, where reversible β-carbon elimination of a spirocyclic [2 + 2] azatitanacyclobutene intermediate is followed by selectivity-determining β-hydrogen elimination of the resulting metallacycle. Further functionalizations of these branched α-methylene imine products are explored, demonstrating their utility as building blocks.

References

Jan 1, 1991·Journal of Neurology·J Olesen
Jan 1, 1986·Journal of Medicinal Chemistry·A StützD Berney
Feb 19, 2002·Chemical Reviews·Mogens Johannsen, Karl Anker Jørgensen
Jan 25, 2008·Nature·Huw M L Davies, James R Manning
Aug 14, 2008·Chemical Reviews·M Mar Díaz-Requejo, Pedro J Pérez
Aug 30, 2008·Chemical Reviews·Thomas E MüllerMizuki Tada
Jan 1, 2010·APMIS : Acta Pathologica, Microbiologica, Et Immunologica Scandinavica·Kok-Fai KongKalai Mathee
Nov 23, 2010·Chemical Society Reviews·Hongjian Lu, X Peter Zhang
Jan 15, 2011·Chemical Society Reviews·Florence ColletPhilippe Dauban
Apr 25, 2013·Journal of the American Chemical Society·Yunzhe JiaoWilliam D Jones
Nov 13, 2013·Chemical Society Reviews·Marie-Laure Louillat, Frederic W Patureau
Dec 24, 2014·Angewandte Chemie·Jacob C TimmermanRoss A Widenhoefer
Aug 22, 2015·Accounts of Chemical Research·Aaron L Odom, Tanner J McDaniel
Jul 2, 2016·Chemical Reviews·Matthew E O'ReillyAdam S Veige
Nov 1, 2016·Journal of the American Chemical Society·Zachary W Davis-GilbertIan A Tonks
Dec 17, 2016·The Journal of Organic Chemistry·Daiki NishikawaMasahiro Miura
Jan 5, 2017·Chemical Reviews·Yoonsu ParkSukbok Chang
Aug 9, 2017·Accounts of Chemical Research·Juliet M AldersonJennifer M Schomaker
Aug 11, 2017·Dalton Transactions : an International Journal of Inorganic Chemistry·Zachary W Davis-Gilbert, Ian A Tonks
Aug 16, 2017·Journal of the American Chemical Society·Sudipta PalChristopher Uyeda
Apr 7, 2018·Dalton Transactions : an International Journal of Inorganic Chemistry·Yuan LiuXiaoguang Bao
May 16, 2018·Journal of the American Chemical Society·Zachary W Davis-GilbertIan A Tonks
Apr 17, 2019·Nature Reviews. Chemistry·Evan P BeaumierIan A Tonks

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Citations

Dec 2, 2020·Inorganic Chemistry·Anders ReinholdtDaniel J Mindiola
Aug 24, 2021·Accounts of Chemical Research·Ian A Tonks

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Methods Mentioned

BETA
hydroamination

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