Nitrile assisted, Brønsted acid catalyzed regio and stereoselective diarylphosphonylation of allyl silyl ethers.
We have discovered a mild, catalytic protocol for the regio- and stereoselective synthesis of trisubstituted allyl diarylphosphonates from the corresponding disubstituted allyl silyl ethers, circumventing the challenges related to the preparation and availability of stereodefined trisubstituted olefins. A closely related arylation reaction was also discovered during the methodology development. By simply switching the reaction medium, high phosphonylation/arylation ratios and vice versa can be achieved. This may not be a direct result of changing solvent polarity. The allyl diarylphosphonates were evaluated as carboxylesterase inhibitors, and the screening results revealed that the inhibitory efficiency is highly related to the choice of alkenes and aryl substituents.
Ho
Chun-Yu
CY
Center of Novel Functional Molecules, The Chinese University of Hong Kong, Shatin, New Territories, Hong Kong SAR. jasonhcy@cuhk.edu.hk
Chan
Chun-Wa
CW
Wo
Siu-Kwan
SK
Zuo
Zhong
Z
Chan
Lai-Ying
LY
D002384:Catalysis; D004987:Ethers / Q000737:chemistry*; D009532:Nickel / Q000737:chemistry; D009570:Nitriles / Q000737:chemistry*; D063065:Organophosphonates / Q000737:chemistry*; D017905:Phosphites / Q000737:chemistry; D012821:Silanes / Q000737:chemistry*; D013237:Stereoisomerism; D013379:Substrate Specificity
D004987:Ethers; D009570:Nitriles; D063065:Organophosphonates; D017905:Phosphites; D012821:Silanes; D009532:Nickel