Bibliographic Details
| 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] |
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| Database: |
Engineering Source |
