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Memory of axial chirality in aryl radical phosphanylations

Bruch, A and Ambrosius, A and Fröhlich, R and Studer, A and Guthrie, DB and Zhang, H and Curran, DP (2010) Memory of axial chirality in aryl radical phosphanylations. Journal of the American Chemical Society, 132 (33). 11452 - 11454. ISSN 0002-7863

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The rate constant for phosphanylation of an aryl radical with trimethylstannyl diphenylphosphane (Me3SnPPh2) has been measured as kphos ≈ 9 × 108 M-1 s -1. Aryl radicals derived from several axially chiral o-haloanilides are trapped by Me3SnPPh2 with complete retention of axial chirality as shown by oxidation of the phosphanes to give stable, easily analyzed phosphane oxides or sulfides. Double phosphanylations of o,o′-dihaloanilides followed by treatment with H2O2 or S8 in either order give enantiomers of a mixed diphosphane oxide sulfide. Chemodivergent trapping of diastereomers of an N-(cyclohex-2-enyl) anilide anilide is observed. For one isomer, the cyclization precedes the Me3SnPPh2 trapping, while for the other isomer direct trapping with Me3SnPPh2 supersedes the cyclization. The products are chiral triaryl phosphanes, oxides, and sulfides that are potentially interesting ligands in asymmetric catalysis. © 2010 American Chemical Society.


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Item Type: Article
Status: Published
CreatorsEmailPitt UsernameORCID
Bruch, A
Ambrosius, A
Fröhlich, R
Studer, A
Guthrie, DB
Zhang, H
Curran, DPcurran@pitt.eduCURRAN
Date: 25 August 2010
Date Type: Publication
Journal or Publication Title: Journal of the American Chemical Society
Volume: 132
Number: 33
Page Range: 11452 - 11454
DOI or Unique Handle: 10.1021/ja105070k
Schools and Programs: Dietrich School of Arts and Sciences > Chemistry
Refereed: Yes
ISSN: 0002-7863
PubMed ID: 20666512
Date Deposited: 08 Feb 2013 20:58
Last Modified: 22 Jun 2021 12:56


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