Sahasrabudhe, Kiran ; Gracias, Vijaya ; Furness, Kelly ; Smith, Brenton T. ; Katz, Christopher E. ; Reddy, D. Srinivasa ; Aubé, Jeffrey (2003) Asymmetric Schmidt Reaction of Hydroxyalkyl Azides with Ketones Journal of the American Chemical Society, 125 (26). pp. 7914-7922. ISSN 0002-7863
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Official URL: http://doi.org/10.1021/ja0348896
Related URL: http://dx.doi.org/10.1021/ja0348896
Abstract
An asymmetric equivalent of the Schmidt reaction permits stereocontrol in ring expansions of symmetrical cyclohexanones. The procedure involves the reaction of chiral 1,2- and 1,3-hydroxyalkyl azides with ketones under acid catalysis; the initial reaction affords an iminium ether that can be subsequently opened with base. A systematic study of this reaction is reported, in which ketone substrates, chiral hydroxyalkyl azides, and reaction conditions are varied. Selectivities as high as ca. 98:2 are possible for the synthesis of substituted caprolactams, with up to 1,7-stereoselection involved in the overall process. The fact that either possible migrating carbon is electronically identical provides an unusual opportunity to study a ring-expansion reaction controlled entirely by stereoelectronic factors. The mechanism of the reaction and the source of its stereoselectivity are also discussed.
Item Type: | Article |
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Source: | Copyright of this article belongs to American Chemical Society |
ID Code: | 122028 |
Deposited On: | 27 Jul 2021 10:36 |
Last Modified: | 27 Jul 2021 10:36 |
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