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One product, two pathways: Initially divergent radical reactions reconverge to form a single product in high yield

Bruch, A and Fröhlich, R and Grimme, S and Studer, A and Curran, DP (2011) One product, two pathways: Initially divergent radical reactions reconverge to form a single product in high yield. Journal of the American Chemical Society, 133 (40). 16270 - 16276. ISSN 0002-7863

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The paper describes examples of net diastereotopic-group-selective radical processes having the unusual feature that a single product is formed even though the key reaction of the two diastereotopic radical precursors is nonselective. For example, reaction of (R)-N-(cyclohex-2-en-1-yl)-N-(2,6-diiodo-4- methylphenyl)acetamide with tributyltin hydride produces 1-((4aR,9aR)-6-methyl- 2,3,4,4a-tetrahydro-1H-carbazol-9(9aH)-yl)ethanone with high product selectivity and in high yield. Analysis of the concentration profiles of the closed-shell intermediates at the halfway point of the reaction shows that nonselective abstraction of diastereotopic iodides by tin radicals occurs, leading to diastereomeric aryl radicals. These isomeric intermediates evolve via two nonintersecting reaction pathways, cyclization and bimolecular trapping or vice versa, into the same final product. Origins of the selectivity are suggested on the basis of conformational analysis of the products using both X-ray crystallography and density functional theory calculations. © 2011 American Chemical Society.


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Item Type: Article
Status: Published
CreatorsEmailPitt UsernameORCID
Bruch, A
Fröhlich, R
Grimme, S
Studer, A
Curran, DPcurran@pitt.eduCURRAN
Date: 12 October 2011
Date Type: Publication
Journal or Publication Title: Journal of the American Chemical Society
Volume: 133
Number: 40
Page Range: 16270 - 16276
DOI or Unique Handle: 10.1021/ja2070347
Schools and Programs: Dietrich School of Arts and Sciences > Chemistry
Refereed: Yes
ISSN: 0002-7863
PubMed ID: 21882875
Date Deposited: 15 Nov 2012 19:17
Last Modified: 02 Feb 2019 15:58


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