Nonenzymatic Acylative Kinetic Resolution of Baylis-Hillman Adducts

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• 作者：Ciar&aacute ; n Ó ; D&aacute ; laigh ; Stephen J. Connon
• 刊名：Journal of Organic Chemistry
• 出版年：2007
• 出版时间：August 31, 2007
• 年：2007
• 卷：72
• 期：18
• 页码：7066 - 7069
• 全文大小：84K
• 年卷期：v.72,no.18(August 31, 2007)
• ISSN：1520-6904

文摘

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The first efficient nonenzymatic acylative kinetic resolutionof Baylis-Hillman adducts is reported. Chiral pyridinecatalyst 1a and an optimized analogue 1e are capable ofpromoting the synthetically useful enantioselective acylation(the efficiency of which is outstanding for sp²-sp² carbinolsubstrates, s = 3.5-13.1, ee up to 97%) of Baylis-Hillmanadducts derived from recalcitrant precursors which arecurrently difficult to synthesize utilizing benchmark asymmetric Baylis-Hillman reaction catalyst technology. A novelone-pot synthesis-kinetic resolution process involving aDBU-catalyzed Baylis-Hillman reaction and subsequent 1e/DBU-mediated enantioselective acylation has also beendeveloped.