Journal article
Reactions of (organostannyl)- and (organogermyl)lithium reagents with some (allylic) cyclohex-2-enyl chlorides
Journal of Organic Chemistry, Vol.47(25), pp.4884-4895
1982
Abstract
The stereo- and regiochemistries of the reactions between (trimethylgermyl)lithium, (triphenylstannyl)lithium, and (trimethylstannyl)lithium and cis- and trans-5-methyl-2-cyclohexenyl chlorides, 3,5-dimethyl-2-cyclohexenyl chlorides, and some deuterated derivatives have been investigated utilizing 1H, 2H, 13C, and 119Sn nuclear magnetic resonance spectroscopy. The major substitution pathway (forming the allylic organometallic) involves configurational inversion at carbon and is accompanied by an insignificant level of 2H relocation between the allylic positions. The 8N2 mechanism is strongly implicated. Serious side reactions accompany the reactions of (trimethylgermyl)lithium generated in hexamethylphosphoric triamide (HMPA), and significant amounts of digermanes and cyclohexenyldimethylamines form. The latter almost certainly result from chloride displacement by dimethylamide ((CH3)2N:-, formed by alkali metal cleavage of HMPA), such displacement proceeding regio- and stereospecifically in accord with the SN2 pathway. Pentamethyl(cyclohex-2-enyl)digermanes which are formed stereospecifically, are considered to result from chloride displacement by (pentamethyldigermyl)lithium, formed by dimethylgermylene insertion into (trimethylgermyl)lithium itself. Certain redistribution reactions of the pentamethyl(cyclohex-2-enyl)digermanes have been observed. © 1982 American Chemical Society.
Details
- Title
- Reactions of (organostannyl)- and (organogermyl)lithium reagents with some (allylic) cyclohex-2-enyl chlorides
- Authors
- G Wickham (Author) - University of QueenslandDavid James Young (Author) - University of QueenslandW Kitching (Author) - University of Queensland
- Publication details
- Journal of Organic Chemistry, Vol.47(25), pp.4884-4895
- Publisher
- American Chemical Society
- Date published
- 1982
- DOI
- 10.1021/jo00146a014
- ISSN
- 0022-3263
- Organisation Unit
- University of the Sunshine Coast, Queensland
- Language
- English
- Record Identifier
- 99449293202621
- Output Type
- Journal article
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