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Intramolecular Diels-Alder Reactions of Cycloalkenones: Stereoselectivity, Lewis Acid Acceleration, and Halogen Substituent Effects

Pham, HV and Paton, RS and Ross, AG and Danishefsky, SJ and Houk, KN (2014) Intramolecular Diels-Alder Reactions of Cycloalkenones: Stereoselectivity, Lewis Acid Acceleration, and Halogen Substituent Effects. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY. pp. 2397-2403.

Abstract

The intramolecular Diels-Alder reactions of cycloalkenones and terminal dienes occur with high endo stereoselectivity, both thermally and under Lewis-acidic conditions. Through computations, we show that steric repulsion and tether conformation govern the selectivity of the reaction, and incorporation of either BF3 or alpha-halogenation increases the rate of cycloaddition. With a longer tether, isomerization from a terminal diene to the more stable internal diene results in a more facile cycloaddition

Item Type: Article
Additional Information: NIBR author: Ross, AG institute: NIBR- address only contributor address: Univ Calif Los Angeles, Dept Chem & Biochem, Los Angeles, CA 90095 USA houk@chem.ucla.edu; Univ Calif Los Angeles, Dept Chem & Biochem, Los Angeles, CA 90095 USA, Univ Oxford, Chem Res Lab, Oxford OX1 3TA, England robert.paton@chem.ox.ac.uk; Columbia Univ, Dept Chem, New York, NY 10027 USA, Novartis Inst BioMedical Res Inc, Cambridge, MA 02139 USA ; Columbia Univ, Dept Chem, New York, NY 10027 USA, Sloan Kettering Inst Canc Res, Bioorgan Chem Lab, New York, NY 10065 USA s.danishefsky@ski.mskcc.org; Univ Calif Los Angeles, Dept Chem & Biochem, Los Angeles, CA 90095 USA; Paton, R S; Univ Calif Los Angeles, Dept Chem & Biochem, 607 Charles E Young Dr, Los Angeles, CA 90095 USA
Date Deposited: 13 Oct 2015 13:12
Last Modified: 13 Oct 2015 13:12
URI: https://oak.novartis.com/id/eprint/22661

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