A Family of -macrocyclic Diphosphines: Modular, Stereoselective Synthesis and Application in Catalytic CO/ethylene Coupling

Overview

Journal Chem Sci

Publisher Royal Society of Chemistry

Specialty Chemistry

Date 2017 Jun 16

PMID 28616145

Citations 1

Authors

Ioana Knopf

Daniel Tofan

Dirk Beetstra

Abdulaziz Al-Nezari

Khalid Al-Bahily

Christopher C Cummins

Affiliations

Soon will be listed here.

Abstract

A family of -macrocyclic diphosphines was prepared in just three steps from white phosphorus and commercial materials using a modular synthetic approach. Alkylation of bicyclic diphosphane 3,4,8,9-tetramethyl-1,6-diphosphabicyclo(4.4.0)deca-3,8-diene, or P(dmb), produced phosphino-phosphonium salts [R-P(dmb)]X, where R is methyl, benzyl and isobutyl, in yields of 90-96%. Treatment of these salts with organolithium or Grignard reagents yielded symmetric and unsymmetric macrocyclic diphosphines of the form -1-R-6-R'-3,4,8,9-tetramethyl-2,5,7,10-tetrahydro-1,6-DiPhospheCine, or R,R'-DPC, in which R' is methyl, cyclohexyl, phenyl or mesityl, in yields of 46-94%. Alternatively, symmetric diphosphine Cy-DPC was synthesized in 74% yield from the dichlorodiphosphine ClP(dmb). As a first application, these -macrocyclic diphosphines were used as ligands in the nickel-catalyzed synthesis of acrylate from CO and ethylene, for which they showed promising catalytic activity.

Citing Articles

Functionalization of P through Direct P-C Bond Formation.

Borger J, Ehlers A, Chris Slootweg J, Lammertsma K Chemistry. 2017; 23(49):11738-11746.

PMID: 28497639 PMC: 5655700. DOI: 10.1002/chem.201702067.

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