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Clarification of the Stereochemical Course of Nucleophilic Substitution of Arylsulfonate-Based Nucleophile Assisting Leaving Groups.

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Title: Clarification of the Stereochemical Course of Nucleophilic Substitution of Arylsulfonate-Based Nucleophile Assisting Leaving Groups.
Authors: Braddock, D. Christopher1 c.braddock@imperial.ac.uk, Pouwer, Rebecca H.1, Burton, Jonathan W.2 jonathan.burton@chem.ox.ac.uk, Broadwith, Phillip2
Source: Journal of Organic Chemistry. 8/21/2009, Vol. 74 Issue 16, p6042-6049. 8p. 3 Charts.
Subjects: Alcohol research, Chemical reactions, Carbocations, Sulfonates, Acetone, Stereochemistry
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 TiCI4, 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 SN1 mechanism. [ABSTRACT FROM AUTHOR]
Copyright of Journal of Organic Chemistry is the property of American Chemical Society and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)
Database: Engineering Source
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DbLabel: Engineering Source
An: 44221442
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  Data: Clarification of the Stereochemical Course of Nucleophilic Substitution of Arylsulfonate-Based Nucleophile Assisting Leaving Groups.
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  Data: <searchLink fieldCode="AR" term="%22Braddock%2C+D%2E+Christopher%22">Braddock, D. Christopher</searchLink><relatesTo>1</relatesTo><i> c.braddock@imperial.ac.uk</i><br /><searchLink fieldCode="AR" term="%22Pouwer%2C+Rebecca+H%2E%22">Pouwer, Rebecca H.</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Burton%2C+Jonathan+W%2E%22">Burton, Jonathan W.</searchLink><relatesTo>2</relatesTo><i> jonathan.burton@chem.ox.ac.uk</i><br /><searchLink fieldCode="AR" term="%22Broadwith%2C+Phillip%22">Broadwith, Phillip</searchLink><relatesTo>2</relatesTo>
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  Data: <searchLink fieldCode="JN" term="%22Journal+of+Organic+Chemistry%22">Journal of Organic Chemistry</searchLink>. 8/21/2009, Vol. 74 Issue 16, p6042-6049. 8p. 3 Charts.
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  Data: <searchLink fieldCode="DE" term="%22Alcohol+research%22">Alcohol research</searchLink><br /><searchLink fieldCode="DE" term="%22Chemical+reactions%22">Chemical reactions</searchLink><br /><searchLink fieldCode="DE" term="%22Carbocations%22">Carbocations</searchLink><br /><searchLink fieldCode="DE" term="%22Sulfonates%22">Sulfonates</searchLink><br /><searchLink fieldCode="DE" term="%22Acetone%22">Acetone</searchLink><br /><searchLink fieldCode="DE" term="%22Stereochemistry%22">Stereochemistry</searchLink>
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  Data: 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 TiCI4, 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 SN1 mechanism. [ABSTRACT FROM AUTHOR]
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  Data: <i>Copyright of Journal of Organic Chemistry is the property of American Chemical Society and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract.</i> (Copyright applies to all Abstracts.)
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        Value: 10.1021/jo900991z
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      – Code: eng
        Text: English
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      – SubjectFull: Chemical reactions
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      – SubjectFull: Carbocations
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      – SubjectFull: Sulfonates
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      – SubjectFull: Acetone
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      – TitleFull: Clarification of the Stereochemical Course of Nucleophilic Substitution of Arylsulfonate-Based Nucleophile Assisting Leaving Groups.
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              Text: 8/21/2009
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