期刊
JOURNAL OF ORGANIC CHEMISTRY
卷 73, 期 21, 页码 8537-8544出版社
AMER CHEMICAL SOC
DOI: 10.1021/jo801736x
关键词
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资金
- NSF [CHE-0517876]
- PRF [37969-GB4]
- Research Corporation [CC5551]
- Barnard College
- Barnard Chemistry Department
- Bernice Segal Fellowship
- Office of the Dean of Students of Barnard College
Dichloro- and phenylchlorocarbene (CCl2 and PhCCl) add to cyclooctyne via a barrierless process (MP2/ 6-311 +G*, B3LYP/6-311+G*, B3LYP/6-31G*) to yield the expected corresponding cyclopropene adducts. A three-dimensional potential energy surface (PES) for CCl2 addition to cyclooctyne (B3LYP/6-31G*) shows the formation of the cyclopropene product and also possible formation of a vinylcarbene. Residing in a shallow energy well, the vinylcarbene easily rearranges to the cyclopropene, product, or to an exocyclic vinyl bicycio[3.3.0] octane. Although the calculated three-dimensional PES indicates possible dynamic control of the cyclooctyne-chlorocarbene system through the putative formation of a vinylcarbene (ill addition to the expected cyclopropene). additional calculations and preliminary experimental work show paths through the vinylcarbene to be unlikely. If the additions of chlorocarbenes to cyclooctyne are controlled by reaction dynamics, we predict that the vast majority of the reactions proceed via traditional carbene cycloaddition with only a very minor amount of products formed from the alternative pathway.
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