1,2- and 1,5-Stereocontrols in 5-Hexenyl Radical Cyclizations: Cooperative or Antagonist Effect. Confrontation of Experimental Results with MM2 Calculations of Transition States

M. P. Bertrand; I. De Riggi; C. Lesueur; S. Gastaldi; R. Nouguier; C. Jaime; A. Virgili

doi:10.1021/jo00124a012

1,2- and 1,5-Stereocontrols in 5-Hexenyl Radical Cyclizations: Cooperative or Antagonist Effect. Confrontation of Experimental Results with MM2 Calculations of Transition States

M. P. Bertrand, I. De Riggi, C. Lesueur, S. Gastaldi, R. Nouguier, C. Jaime, A. Virgili

Department of Chemistry

Research output: Contribution to journal › Article › Research › peer-review

19 Citations (Scopus)

Abstract

The cyclofunctionalization of 1,6-dienes 1 and 2 via the addition of tosyl radical allows the analysis of the combined effects of 1,2- and 1,5-stereocontrols on the outcome of 5-hexenyl radical cyclizations. MM2 calculations of transition states agree quite well with the experimental selectivity, i.e., exclusive 1,2-trans control, and predominance of 1,5-cis over 1,5-trans relationship. The addition of TsBr to carbohydrate-derived epimeric dienes 3a and 3b shows that the stereochemistry of the newly formed C—C bond is controlled by the configuration of the C2 center of the radical. 1,5-trans or 1,5-cis selectivity can be achieved depending on the configuration of C2. © 1995, American Chemical Society. All rights reserved.

Original language	English
Pages (from-to)	6040-6045
Journal	Journal of Organic Chemistry
Volume	60
Issue number	19
DOIs	https://doi.org/10.1021/jo00124a012
Publication status	Published - 1 Sep 1995

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@article{1fcb01864f444e93b9007bc870d16e5c,

title = "1,2- and 1,5-Stereocontrols in 5-Hexenyl Radical Cyclizations: Cooperative or Antagonist Effect. Confrontation of Experimental Results with MM2 Calculations of Transition States",

abstract = "The cyclofunctionalization of 1,6-dienes 1 and 2 via the addition of tosyl radical allows the analysis of the combined effects of 1,2- and 1,5-stereocontrols on the outcome of 5-hexenyl radical cyclizations. MM2 calculations of transition states agree quite well with the experimental selectivity, i.e., exclusive 1,2-trans control, and predominance of 1,5-cis over 1,5-trans relationship. The addition of TsBr to carbohydrate-derived epimeric dienes 3a and 3b shows that the stereochemistry of the newly formed C—C bond is controlled by the configuration of the C2 center of the radical. 1,5-trans or 1,5-cis selectivity can be achieved depending on the configuration of C2. {\textcopyright} 1995, American Chemical Society. All rights reserved.",

author = "Bertrand, {M. P.} and {De Riggi}, I. and C. Lesueur and S. Gastaldi and R. Nouguier and C. Jaime and A. Virgili",

year = "1995",

month = sep,

day = "1",

doi = "10.1021/jo00124a012",

language = "English",

volume = "60",

pages = "6040--6045",

journal = "Journal of Organic Chemistry",

issn = "0022-3263",

publisher = "American Chemical Society",

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}

Bertrand, MP, De Riggi, I, Lesueur, C, Gastaldi, S, Nouguier, R, Jaime, C & Virgili, A 1995, '1,2- and 1,5-Stereocontrols in 5-Hexenyl Radical Cyclizations: Cooperative or Antagonist Effect. Confrontation of Experimental Results with MM2 Calculations of Transition States', Journal of Organic Chemistry, vol. 60, no. 19, pp. 6040-6045. https://doi.org/10.1021/jo00124a012

1,2- and 1,5-Stereocontrols in 5-Hexenyl Radical Cyclizations: Cooperative or Antagonist Effect. Confrontation of Experimental Results with MM2 Calculations of Transition States. / Bertrand, M. P.; De Riggi, I.; Lesueur, C.; Gastaldi, S.; Nouguier, R.; Jaime, C.; Virgili, A.

In: Journal of Organic Chemistry, Vol. 60, No. 19, 01.09.1995, p. 6040-6045.

Research output: Contribution to journal › Article › Research › peer-review

TY - JOUR

T1 - 1,2- and 1,5-Stereocontrols in 5-Hexenyl Radical Cyclizations: Cooperative or Antagonist Effect. Confrontation of Experimental Results with MM2 Calculations of Transition States

AU - Bertrand, M. P.

AU - De Riggi, I.

AU - Lesueur, C.

AU - Gastaldi, S.

AU - Nouguier, R.

AU - Jaime, C.

AU - Virgili, A.

PY - 1995/9/1

Y1 - 1995/9/1

N2 - The cyclofunctionalization of 1,6-dienes 1 and 2 via the addition of tosyl radical allows the analysis of the combined effects of 1,2- and 1,5-stereocontrols on the outcome of 5-hexenyl radical cyclizations. MM2 calculations of transition states agree quite well with the experimental selectivity, i.e., exclusive 1,2-trans control, and predominance of 1,5-cis over 1,5-trans relationship. The addition of TsBr to carbohydrate-derived epimeric dienes 3a and 3b shows that the stereochemistry of the newly formed C—C bond is controlled by the configuration of the C2 center of the radical. 1,5-trans or 1,5-cis selectivity can be achieved depending on the configuration of C2. © 1995, American Chemical Society. All rights reserved.

AB - The cyclofunctionalization of 1,6-dienes 1 and 2 via the addition of tosyl radical allows the analysis of the combined effects of 1,2- and 1,5-stereocontrols on the outcome of 5-hexenyl radical cyclizations. MM2 calculations of transition states agree quite well with the experimental selectivity, i.e., exclusive 1,2-trans control, and predominance of 1,5-cis over 1,5-trans relationship. The addition of TsBr to carbohydrate-derived epimeric dienes 3a and 3b shows that the stereochemistry of the newly formed C—C bond is controlled by the configuration of the C2 center of the radical. 1,5-trans or 1,5-cis selectivity can be achieved depending on the configuration of C2. © 1995, American Chemical Society. All rights reserved.

U2 - 10.1021/jo00124a012

DO - 10.1021/jo00124a012

M3 - Article

VL - 60

SP - 6040

EP - 6045

JO - Journal of Organic Chemistry

JF - Journal of Organic Chemistry

SN - 0022-3263

IS - 19

ER -

1,2- and 1,5-Stereocontrols in 5-Hexenyl Radical Cyclizations: Cooperative or Antagonist Effect. Confrontation of Experimental Results with MM2 Calculations of Transition States

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