对于高度选择区域的内部烯的异构化-水合成型的四联体
Yongjun Yan1, Xiaowei Zhang, Xumu Zhang
1Department of Chemistry, The Pennsylvania State University, University Park, Pennsylvania 16802, USA.
Journal of the American Chemical Society
|December 15, 2006
概括
合成了一种新的四联体,使多种协调模式成为可能. 这种新配体在涉及内部烯酸的催化反应中提高了区域选择性,超过了其双对应物.
科学领域:
- 有机金属化学 有机金属化学
- 催化剂是一种催化剂.
- 连接体设计 连接体设计
背景情况:
- 开发新的基于的配体对于推进同质催化非常重要.
- 与传统的双联体相比,四联体提供了独特的协调可能性.
- 甲基化反应中的区域选择性仍然是一个关键的挑战,特别是在内部烯酸中.
研究的目的:
- 为了合成和表征一种新的基于pyrrole的四酸连接体.
- 为了研究新配体的化模式和催化性能.
- 为了比较使用四联体与双类似物的催化异构化-水合形成的区域选择性.
主要方法:
- 合成一种新的以醇为基础的四酸连接体.
- 使用光谱技术进行表征 (NMR,质谱学).
- 催化异构化-内部烯酸的水合成型.
主要成果:
- 成功制备了四酸连接体.
- 通过连接体证明了多种化模式.
- 与双相应物相比,在催化内部烯酸的异构化-水合形成过程中实现了更高的区域选择性.
结论:
- 这种新的以醇为基础的四联体在催化甲基化中是有效的.
- 酸连接体促进了对内部烯的增强区域选择性.
- 这项研究突显了多牙联体在催化中的潜力.
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Hydroboration proceeds in a concerted fashion with the attack of borane on the π bond, giving a cyclic four-centered transition state. The –BH2 group is bonded to the less substituted carbon and –H to the more substituted carbon. The concerted nature requires the simultaneous addition of –H and –BH2 across the same face of the alkene giving syn stereochemistry.
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In addition to the oxymercuration–demercuration method, which converts the alkenes to alcohols with Markovnikov orientation, a complementary hydroboration-oxidation method yields the anti-Markovnikov product. The hydroboration reaction, discovered in 1959 by H.C. Brown, involves the addition of a B–H bond of borane to an alkene giving an organoborane intermediate. The oxidation of this intermediate with basic hydrogen peroxide forms an alcohol.
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Introduction
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