Efficient Asymmetric Synthesis
of P‑Chiral Phosphine Oxides via Properly
Designed and Activated
Benzoxazaphosphinine-2-oxide Agents

Han, Zhengxu S.; Goyal, Navneet; Herbage, Melissa A.; Sieber, Joshua
D.; Qu, Bo; Xu, Yibo; Li, Zhibin,; Reeves, Jonathan T.; Desrosiers, Jean-Nicolas; Ma, Shengli; Grinberg, Nelu; Lee, Heewon; P. R. Mangunuru, Hari; Zhang, Yongda; Krishnamurthy, Dhileep; Lu, Bruce
Z.; Song, Jinhua J.; Wang, Guijun; Senanayake, Chris H.

doi:10.1021/ja312352p.s008

ja312352p_si_008.pdf (1.77 MB)

Efficient Asymmetric Synthesis of P‑Chiral Phosphine Oxides via Properly Designed and Activated Benzoxazaphosphinine-2-oxide Agents

journal contribution

posted on 2016-02-19, 22:05 authored by Zhengxu S. Han, Navneet Goyal, Melissa A. Herbage, Joshua D. Sieber, Bo Qu, Yibo Xu, Zhibin, Li, Jonathan T. Reeves, Jean-Nicolas Desrosiers, Shengli Ma, Nelu Grinberg, Heewon Lee, Hari P. R. Mangunuru, Yongda Zhang, Dhileep Krishnamurthy, Bruce Z. Lu, Jinhua J. Song, Guijun Wang, Chris H. Senanayake

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.