Carreira, Erick M. and Hastings, Curtis A. and Shepard, Mary S. and Yerkey, Lori A. and Millward, Dan B. (1994) Asymmetric Induction in Intramolecular [2 + 2]-Photocycloadditions of 1,3-Disubstituted Allenes with Enones and Enoates. Journal of the American Chemical Society, 116 (15). pp. 6622-6630. ISSN 0002-7863. https://resolver.caltech.edu/CaltechAUTHORS:20180601-151522887
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Abstract
Irradiation of optically active allenes (89-92% ee) appended to enones and enoates affords alkylidenecyclobutane photoadducts with high levels of asymmetric induction (83-100%) derived exclusively from the allene fragment. The substrates studied include allenes tethered to enones such as 1,3-cyclohexanedionea nd 1,3-cyclopentanedione, as well as allenes tethered to functionalized coumarins. The enantiomer ratios of the photoadducts were quantified by derivatization of the products as the corresponding Mosher MTPA esters and analysis by ^1H NMR spectroscopy. The exo-methylenecyclobutanes obtained upon irradiation of allene-mumarins are isolated as single olefin diastereomers. Irradiation of a coumarin tethered at C(5) with an optically active allene affords an alkynyl-substituted oxepane with complete asymmetric induction.
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Additional Information: | © 1994 American Chemical Society. Received January 3, 1994. C.A.H. thanks W. R. Grace and Co. for a summer fellowship award. M.S.S. is grateful to the Office of Naval Research for a graduate fellowship. We are grateful to Professor K. I. Hardcastle (California State University, Northridge) for obtaining an X-ray crystal structure of (±)-25. This research has been supported by a Beckman Young Investigator Award, the National Science Foundation (CHE-9221945), and a Camille and Henry Dreyfus New Faculty Award (NF-92-46). | ||||||||||||
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Issue or Number: | 15 | ||||||||||||
Record Number: | CaltechAUTHORS:20180601-151522887 | ||||||||||||
Persistent URL: | https://resolver.caltech.edu/CaltechAUTHORS:20180601-151522887 | ||||||||||||
Official Citation: | Asymmetric Induction in Intramolecular [2 + 2]-Photocycloadditions of 1,3-Disubstituted Allenes with Enones and Enoates Erick M. Carreira, Curtis A. Hastings, Mary S. Shepard, Lori A. Yerkey, and Dan B. Millward Journal of the American Chemical Society 1994 116 (15), 6622-6630 DOI: 10.1021/ja00094a017 | ||||||||||||
Usage Policy: | No commercial reproduction, distribution, display or performance rights in this work are provided. | ||||||||||||
ID Code: | 86758 | ||||||||||||
Collection: | CaltechAUTHORS | ||||||||||||
Deposited By: | George Porter | ||||||||||||
Deposited On: | 01 Jun 2018 22:56 | ||||||||||||
Last Modified: | 09 Mar 2020 13:18 |
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