Efficient Asymmetric Synthesis of P-Chiral Phosphine Oxides via Properly Designed and Activated Benzoxazaphosphinine-2-oxide Agents
Efficient Asymmetric Synthesis of P-Chiral Phosphine Oxides via Properly Designed and Activated Benzoxazaphosphinine-2-oxide Agents
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DOI：
10.1021/ja312352p
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发表时间：
2013-02-20
影响因子：
15
通讯作者：
Senanayake, Chris H.
中科院分区：
文献类型：
--
作者：
Han, Zhengxu S.;Goyal, Navneet;Senanayake, Chris H.
发展了一种通用、高效和高度非对映选择性的方法来合成结构和空间上不同的对手性膦氧化物。该方法依赖于多功能手性膦转移试剂1，3，2-苯并恶杂膦-2-氧化物上的顺序亲核取代，该试剂具有增强和区分P-N和P-O键的亲核性。这两个键的反应性都经过微调，即使在温和的条件下，也可以与空间受阻的亲核试剂发生裂解。
A general, efficient, and highly diastereoselective method for the synthesis of structurally and sterically diverse P-chiral phosphine oxides was developed. The method relies on sequential nucleophilic substitution on the versatile chiral phosphinyl transfer agent 1,3,2-benzoxazaphosphinine-2-oxide, which features enhanced and differentiated P N and P-O bond reactivity toward nucleophiles. The reactivities of both bonds are fine-tuned to allow cleavage to occur even with sterically hindered nucleophiles under mild conditions.