A Primary Acyl Phosphine Stabilized by a Phosphonium Ylide. Issue 34 (13th July 2021)

• Record Type: Journal Article
• Authors: Petrone, David A.; Szkop, Kevin M.; Miao, Linkun; St. Onge, Piers; Qu, Zheng‐Wang; Grimme, Stefan; Stephan, Douglas W.
• Is Part Of: Angewandte Chemie international edition. Volume 60:Issue 34(2021)
• Page Start: 18547
• Page End: 18551
• Publication Date: 2021-07-13
• Subjects: betaine -- phosphaketene -- primary acyl phosphines -- reaction mechanism -- ylide; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.202106846
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: Primary acyl‐phosphines are scarce in the literature. Here we show that the reaction of Ph3 GePCO with the ylide Ph3 PCH2 proceeds to give the species Ph3 PCHC(O)PH(GePh3 ) 1 . Deprotonation of 1 with Na[N(SiMe3 )2 ] generates the salt [Na(THF)2 ][Ph3 PCHC(O)P(GePh3 )] 2 which provides subsequent access to the bis ‐germanylated acylphosphine, Ph3 PCHC(O)P(GePh3 )2 3 . Alternatively, treatment of 1 with HCl in dioxane affords the primary acylphosphine Ph3 PCHC(O)PH2 4 . Compound 4 is a rare example of an air stable primary acyl‐phosphines and the first devoid of a stabilizing heteroatom adjacent to the carbonyl fragment. Abstract : The reaction of Ph3 GePCO with the ylide Ph3 PCH2 and subsequent reactions are used to access Ph3 PCHC(O)P(GePh3 )2 and Ph3 PCHC(O)PH2 . The zwitterionic nature of these species illustrates this new strategy to stabilization of acylphosphines. Indeed the latter species is a rare example of an air stable primary acyl‐phosphine, devoid of a stabilizing heteroatom adjacent to the carbonyl fragment.