Journal article

Clarification of the stereochemical course of nucleophilic substitution of arylsulfonate-based nucleophile assisting leaving groups.

Abstract:: Secondary alcohols modified as tosylates, PEG-sulfonates, or quisylates undergo inversion of configuration at the reacting center when treated with lithium halide in acetone at reflux, where the PEG-sulfonates and quisylates are substantially more reactive. In sterically hindered cases, elimination is a competing process. In contrast, when treated with TiCl(4), simple secondary sulfonates give chloride products with partial inversion of configuration. Any observed retention of configuration in a given alkyl sulfonate substrate under these conditions is likely due to neighboring group participation or diastereoselective attack on a carbocation (or ion pair) rather than an S(N)i mechanism.

Publication status:: Published

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APA Style

Braddock, D., Pouwer, R., Burton, J., & Broadwith, P. (2009). Clarification of the stereochemical course of nucleophilic substitution of arylsulfonate-based nucleophile assisting leaving groups. Journal of Organic Chemistry, 74(16), 6042–6049.

MLA Style

Braddock, D, et al. “Clarification of the Stereochemical Course of Nucleophilic Substitution of Arylsulfonate-Based Nucleophile Assisting Leaving Groups.” Journal of Organic Chemistry, vol. 74, no. 16, 2009, pp. 6042–49.

Chicago Style

Braddock, D, R Pouwer, J Burton, and P Broadwith. 2009. “Clarification of the Stereochemical Course of Nucleophilic Substitution of Arylsulfonate-Based Nucleophile Assisting Leaving Groups.” Journal of Organic Chemistry 74 (16): 6042–49.
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Publisher copy:: 10.1021/jo900991z

Authors

+ Braddock, D More by this author

Role:: Author

+ Pouwer, R More by this author

Role:: Author

+ Burton, J More by this author

Institution:: University of Oxford
Division:: MPLS
Department:: Chemistry
Sub department:: Organic Chemistry
Role:: Author

+ Broadwith, P More by this author

Role:: Author

Journal:: Journal of organic chemistry More from this journal
Volume:: 74
Issue:: 16
Pages:: 6042-6049
Publication date:: 2009-08-01
DOI:: 10.1021/jo900991z
EISSN:: 1520-6904
ISSN:: 0022-3263

Language:: English
Pubs id:: pubs:41360
UUID:: uuid:2d9f1400-f9e9-4ab2-ad8d-6b95cc244f54
Local pid:: pubs:41360
Source identifiers:: 41360
Deposit date:: 2012-12-19
ARK identifier:: ark:/29072/ora_2d9f1400f9e94ab2ad8d6b95cc244f54

Terms of use

Copyright date:: 2009

Licence:: Terms and Conditions of Use for Oxford University Research Archive

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