Towards a General Understanding of Carbonyl‐Stabilised Ammonium Ylide‐Mediated Epoxidation Reactions
نویسندگان
چکیده
The key factors for carbonyl-stabilised ammonium ylide-mediated epoxidation reactions were systematically investigated by experimental and computational means and the hereby obtained energy profiles provide explanations for the observed experimental results. In addition, we were able to identify the first tertiary amine-based chiral auxiliary that allows for high enantioselectivities and high yields for such epoxidation reactions.
منابع مشابه
On the origin of the stereoselectivity in chiral amide-based ammonium ylide-mediated epoxidations
ABSTRACT Detailed DFT studies provide an in-depth mechanistic understanding for the use of chiral amide-based ammonium ylides in epoxidation reactions. It is shown that the used chiral auxiliary efficiently shields one face of the ylide, which thus results in an extraordinarily high stereoselectivity giving only one trans-isomer with perfect control of the absolute configuration. GRAPHICAL AB...
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Article history: Received 13 April 2010 Accepted 28 April 2010 Available online 16 June 2010 Dedicated to Henri Kagan on the occasion of his 80th birthday 0957-4166/$ see front matter 2010 Elsevier Ltd. A doi:10.1016/j.tetasy.2010.04.046 * Corresponding author. Tel.: +44 117 954 6315; fa E-mail address: [email protected] (V.K. Agg The epoxidation of meroquinene aldehyde with a chiral sul...
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