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Bond rotation dynamics of enamides: The effect of the acyl group and potential for chirality transfer during 5-endo trig radical cyclizations

Clark, AJ and Curran, DP and Geden, JV and James, N and Wilson, P (2011) Bond rotation dynamics of enamides: The effect of the acyl group and potential for chirality transfer during 5-endo trig radical cyclizations. Journal of Organic Chemistry, 76 (11). 4546 - 4551. ISSN 0022-3263

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Abstract

Barriers to rotation of the N-alkenyl bond in a series of N-cycloalkenyl-N-benzyl acetamide derivatives have been measured in different solvents by variable-temperature NMR experiments. The barriers range from 9.7 to 14.2 kcal/mol, depending on substituents on the acetamide acyl group. Polar solvents such as chloroform and methanol increase the barrier to rotation compared to nonpolar solvents such as toluene. The barrier to rotation of "mimics" for acetamide-based radicals are estimated. The relative order of the values of krot for different acyl groups parallels their reported Taft Es paramaters. For successful chirality transfer in 5-endo trig radical cyclization, it is evident that rotations would need to be significantly slower than those reported here. © 2011 American Chemical Society.


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Details

Item Type: Article
Status: Published
Creators/Authors:
CreatorsEmailPitt UsernameORCID
Clark, AJ
Curran, DPcurran@pitt.eduCURRAN
Geden, JV
James, N
Wilson, P
Date: 3 June 2011
Date Type: Publication
Journal or Publication Title: Journal of Organic Chemistry
Volume: 76
Number: 11
Page Range: 4546 - 4551
DOI or Unique Handle: 10.1021/jo200343z
Schools and Programs: Dietrich School of Arts and Sciences > Chemistry
Refereed: Yes
ISSN: 0022-3263
PubMed ID: 21506580
Date Deposited: 16 Nov 2012 21:27
Last Modified: 22 Jun 2021 12:56
URI: http://d-scholarship.pitt.edu/id/eprint/16398

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