Enantioselective Alcohol C–H Functionalization for Polyketide Construction: Unlocking Redox-Economy and Site-Selectivity for Ideal Chemical Synthesis

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• 作者：Jiajie Feng ; Zachary A. Kasun ; Michael J. Krische
• 刊名：Journal of the American Chemical Society
• 出版年：2016
• 出版时间：May 4, 2016
• 年：2016
• 卷：138
• 期：17
• 页码：5467-5478
• 全文大小：1390K
• 年卷期：0
• ISSN：1520-5126

文摘

The development and application of stereoselective and site-selective catalytic methods that directly convert lower alcohols to higher alcohols are described. These processes merge the characteristics of transfer hydrogenation and carbonyl addition, exploiting alcohols and π-unsaturated reactants as redox pairs, which upon hydrogen transfer generate transient carbonyl–organometal pairs en route to products of C–C coupling. Unlike classical carbonyl additions, stoichiometric organometallic reagents and discrete alcohol-to-carbonyl redox reactions are not required. Additionally, due to a kinetic preference for primary alcohol dehydrogenation, the site-selective modification of glycols and higher polyols is possible, streamlining or eliminating use of protecting groups. The total syntheses of several iconic type I polyketide natural products were undertaken using these methods. In each case, the target compounds were prepared in significantly fewer steps than previously achieved.