AK-2380GP_published_mainmanuscript - Issue in Honor of...

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Issue in Honor of Prof. Alain Krief ARKIVOC 2007 (x) 365-373 Reactivity of 1-alkyl-2-(bromomethyl)aziridines towards n -butyllithium Matthias D’hooghe and Norbert De Kimpe * Department of Organic Chemistry, Faculty of Bioscience Engineering, Ghent University, Coupure Links 653, B-9000 Ghent, Belgium E-mail: norbert.dekimpe@UGent.be Dedicated to Prof. Alain Krief on the occasion of his 65th birthday Abstract The reactivity of 1-alkyl-2-(bromomethyl)aziridines with regard to n -butyllithium has been evaluated for the first time, resulting in a variety of reaction products due to competitive reaction pathways. The main components in these mixtures are 1-alkyl-2-( N -alkyl- N - allylaminomethyl)aziridines (11-36%), 1-alkyl-2-pentylaziridines (13-26%), N -alkyl- N -allyl- N - butylamines (1-24%), N -alkyl- N -pentylamines (4-12%) and N -alkyl- N -allylamines (1-7%). A few of these components were isolated by means of preparative gas chromatography. The structural identity of some other constituents has been proven by independent syntheses. Keywords: 2-(Bromomethyl)aziridines, ring opening, n -butyllitium Introduction Aziridines are versatile building blocks for the synthesis of a large variety of ring opened and ring expanded amines due to the inherent reactivity of these compounds, 1 an effect undoubtedly resulting from the necessary compression of bond angles in the three-membered ring. Although many reports on the utility of substituted aziridines in organic synthesis are available, 1-alkyl-2- (bromomethyl)aziridines comprise a peculiar and rather unknown class of non-activated aziridine derivatives with high synthetic potential due to three different electrophilic carbon atoms in their structure. 2 As reported before, 1-alkyl-2-(bromomethyl)aziridines are suitable synthetic equivalents for the aziridinylmethyl cation, providing an easy access to 1,2-dialkylaziridines such as 2-ethyl-, 2- pentyl- and 2-(phenylmethyl)aziridines upon treatment with the appropriate lithium dialkylcuprate reagent. 3 A similar reactivity of 1-alkyl-2-(bromomethyl)aziridines has been observed in reaction with oxygen-centered nucleophiles such as alkoxides, phenoxides and ISSN 1424-6376 Page 365 © ARKAT-USA, Inc.
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Issue in Honor of Prof. Alain Krief ARKIVOC 2007 (x) 365-373 carboxylates, affording the corresponding 2-substituted aziridines in a clean and straightforward reaction. 4 Very recently, the reaction of 2-(bromomethyl)aziridines with methyllithium has been reported to afford 1-alkyl-2-( N -alkyl- N -ethylaminomethyl)aziridines through a highly unusual reaction pathway. 5 However, up to now, the reactivity of 1-alkyl-2-(bromomethyl)aziridines with regard to n -butyllithium, a frequently used reagent in organic chemistry, 6 has not been investigated yet, and this will be discussed in the present report.
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This note was uploaded on 02/17/2011 for the course CHEMISTRY 101 taught by Professor Csr during the Spring '11 term at University of Louisville.

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AK-2380GP_published_mainmanuscript - Issue in Honor of...

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