Allylic Phosphorus Ylides Directly Generated from Alcohols with Water as the Only Byproduct

Peizhong Xie; Weishan Fu; Ying Wu; Xinying Cai; Zuolian Sun; Shuangshuang Li; Cuiqing Gao; Xiaobo Yang; Teck-Peng Loh

doi:10.1021/acs.orglett.9b01349

Allylic Phosphorus Ylides Directly Generated from Alcohols with Water as the Only Byproduct

Org Lett. 2019 Jun 7;21(11):4168-4172. doi: 10.1021/acs.orglett.9b01349. Epub 2019 May 28.

Authors

Peizhong Xie¹, Weishan Fu¹, Ying Wu¹, Xinying Cai¹, Zuolian Sun¹, Shuangshuang Li¹, Cuiqing Gao², Xiaobo Yang¹, Teck-Peng Loh^{1

3}

Affiliations

¹ School of Chemistry and Molecular Engineering, Institute of Advanced Synthesis, Jiangsu National Synergetic Innovation Center for Advanced Materials , Nanjing Tech University , Nanjing 211816 , P. R. China.
² Co-Innovation Center for the Sustainable Forestry in Southern China, College of Forestry , Nanjing Forestry University , Nanjing , 210037 , China.
³ Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences , Nanyang Technological University , Singapore 637371 , Singapore.

PMID: 31135163
DOI: 10.1021/acs.orglett.9b01349

Abstract

A novel strategy for the preparation of allylic phosphorus ylides directly from Morita-Baylis-Hillman (MBH) alcohols in an environmentally benign manner was developed. With the assistance of a calcium catalyst, the S_N2' process between phosphines and allylic alcohols occurred smoothly, delivering allylic phosphorus salts and calcium-stabilized hydroxide ions. Then, in situ deprotonation gave the allylic phosphorus ylides with water as the only byproduct. Functionalized 1,3-diene moieties can be conveniently obtained by trapping the ylides through a Wittig olefination.