1, 1-Phosphinoboration of diazomethanes. Issue 80 (20th September 2019)

• Record Type: Journal Article
• Authors: Trofimova, Alina; LaFortune, James H. W.; Qu, Zheng-Wang; Westcott, Stephen A.; Stephan, Douglas W.
• Is Part Of: Chemical communications. Volume 55:Issue 80(2019)
• Page Start: 12100
• Page End: 12103
• Publication Date: 2019-09-20
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1039/c9cc06914c
• Languages: English
• ISSNs: 1359-7345

Abstract

Abstract : The reactions of the phosphinoboranes Ph2 PBMes2, Ph2 PBpin, and Ph2 PBcat with the diazomethanes Ph2 CN2, C12 H8 CN2, and EtO2 CCHN2 are shown to give products of 1, 1-phosphinoboration. Abstract : The reactions of the phosphinoboranes Ph2 PBMes2, Ph2 PBpin, and Ph2 PBcat with the diazomethanes Ph2 CN2, C12 H8 CN2, and EtO2 CCHN2 are shown to give products of 1, 1-phosphinoboration. The products (1–6 ) are shown to have PNB linkages with three-coordinate boron centers, whereas the products (EtOOC)CNN(PR2 )(Bpin) (R = Ph 7, t Bu 8) form zwitterionic heterocycles resulting from chelation of the ester carbonyl to boron. DFT calculations show that the reactions are initiated by N-to-B addition followed by 1, 2-phosphinyl shift.