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Molecules 2015, 20(12), 21433-21441;

DFT Studies on the Stereoselectivity of α-Silyloxy Diazoalkane Cycloadditions

Department of Chemistry, University of Illinois at Chicago, 845 West Taylor Street, Chicago 60607, IL, USA
Abbvie Inc., 1 North Waukegan Road, North Chicago 60064, IL, USA
College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou, Zhejiang 325035, China
Authors to whom correspondence should be addressed.
Academic Editor: Mark Rizzacasa
Received: 14 October 2015 / Revised: 18 November 2015 / Accepted: 26 November 2015 / Published: 2 December 2015
(This article belongs to the Special Issue Pericyclic Reactions)
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The intramolecular [3+2] cycloaddition (32CA) of alkene-tethered α-silyloxydiazoalkanes provides variable stereoselectivity in generating bicyclic pyrazolines where the silyloxy group is either syn or anti to the newly formed pyrazoline ring. To elucidate the origin of the stereoselectivity, density functional theory (DFT) calculations were carried out for the energy of each transition state structure (TSs) and product. Steric effects were identified as the major determining factors in the diastereoselectivity of the 32CA reaction with regards to substrate structure (cyclic or acyclic α-silyloxydiazoalkanes). View Full-Text
Keywords: density functional theory; diazoalkane; [3+2] cycloaddition; gauche effect; stereoselectivity density functional theory; diazoalkane; [3+2] cycloaddition; gauche effect; stereoselectivity

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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited (CC BY 4.0).

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O’Connor, M.J.; Liu, H.; Lee, D.; Zhou, T.; Xia, Y. DFT Studies on the Stereoselectivity of α-Silyloxy Diazoalkane Cycloadditions. Molecules 2015, 20, 21433-21441.

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