Stannyl phosphaketene as a synthon for phosphorus analogues of β-lactams

Yong-An Luo; Zhao Zhao; Ting Chen; Yanguo Li; Yufen Zhao; Douglas W Stephan; Yile Wu

doi:10.1039/d3cc03117a

Stannyl phosphaketene as a synthon for phosphorus analogues of β-lactams

Chem Commun (Camb). 2023 Sep 12;59(73):10956-10959. doi: 10.1039/d3cc03117a.

Authors

Yong-An Luo¹, Zhao Zhao¹, Ting Chen¹, Yanguo Li¹, Yufen Zhao¹, Douglas W Stephan^{1

2}, Yile Wu¹

Affiliations

¹ Institute of Drug Discovery Technology, Ningbo University, Ningbo 315211, Zhejiang, China. wuyile@nbu.edu.cn.
² Department of Chemistry, University of Toronto, 80 St. George St, Toronto, ON M5S3H6, Canada. dstephan@chem.utoronto.ca.

PMID: 37608644
DOI: 10.1039/d3cc03117a

Abstract

The reaction of the stannyl phosphaketene (Nacnac)SnPCO 1 (Nacnac = CH{(CMe)(2,6-ⁱPr₂C₆H₃N)}₂) with B(C₆F₅)₃ produced the 1,4-addition product of (Nacnac)SnPCO(B(C₆F₅)₃). However, the corresponding reactions in the presence of dimethyl maleate, diisopropyl fumarate or diethyl-but-2-ynedioate gave [2+2] addition yielding four-membered phosphacycles, ((Nacnac)Sn(MeO₂C))CHPC(OB(C₆F₅)₃)CH(CO₂Me), [(C₆F₅)₃B)PC(OSn)C(CO₂Me)CH(CO₂Me)]₂, (Nacnac)Sn(ⁱPrO₂C)CC(OAl(C₆F₅)₃)P[CH(CO₂ⁱPr)CH₂(CO₂ⁱPr)]CH(CO₂ⁱPr), and (Nacnac)SnP (EtO₂CCC(CO₂Et))CO(B(C₆F₅)₃), respectively. In contrast, the corresponding reaction of phenylacetylene gave the FLP-addition product (Nacnac)SnOC(P)C(Ph)CH(B(C₆F₅)₃). Collectively, this reactivity demonstrates that the stannyl phosphaketene 1 can act as a synthon for P-analogues of β-lactam derivatives.