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Endo entry to the nortricyclyl-norbornenyl cation system: Stereochemistry in the fragmentation of endo-5-norbornenyl-2-oxychlorocarbene

Moss, RA and Fu, X and Sauers, RR and Wipf, P (2005) Endo entry to the nortricyclyl-norbornenyl cation system: Stereochemistry in the fragmentation of endo-5-norbornenyl-2-oxychlorocarbene. Journal of Organic Chemistry, 70 (21). 8454 - 8460. ISSN 0022-3263

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Abstract

Fragmentation of (S)-endo-5-norbornenyl-2-oxychlorocarbene [(S)-8] in cyclohexane-d12 gives ∼20% (S)-endo-2-chloro-5-norbornene [(S)-7] with ∼50% ee, 65-70% (R)-exo-2-chloro-5-norbornene [(R)-4] with >95% ee, and ∼12% (R)-3-nortricyclyl chloride [(R)-5] with ∼22% ee. (Analogous stereochemical results were also obtained starting with the enantiomeric carbene (R)-8.) The (S)-8 to (S)-7 and (S)-8 to (R)-4 conversions are ascribed mainly to retention and inversion SNi transition states, respectively. These have been located by computational methods and are nearly isoenergetic. In more polar solvents (CDCl3 and CD3CN), the fragmentation of (S)-8 increasingly occurs via competitive ion pair pathways in which steroselectivity is diminished, and escape to the norbornenyl-nortricyclyl cation directs the products away from endo-2-chloro-5-norbornene toward exo-chloride 4 and nortricyclyl chloride 5. © 2005 American Chemical Society.


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Details

Item Type: Article
Status: Published
Creators/Authors:
CreatorsEmailPitt UsernameORCID
Moss, RA
Fu, X
Sauers, RR
Wipf, Ppwipf@pitt.eduPWIPF
Date: 14 October 2005
Date Type: Publication
Journal or Publication Title: Journal of Organic Chemistry
Volume: 70
Number: 21
Page Range: 8454 - 8460
DOI or Unique Handle: 10.1021/jo051222o
Schools and Programs: Dietrich School of Arts and Sciences > Chemistry
Refereed: Yes
ISSN: 0022-3263
PubMed ID: 16209591
Date Deposited: 31 Oct 2013 18:13
Last Modified: 02 Feb 2019 15:57
URI: http://d-scholarship.pitt.edu/id/eprint/19945

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