Chemistry of difluorocarbene adducts to sterically hindered acetylenes

Anderson, Patrick N.; Crabbé, Pierre; Cross, A. D.; Fried, J. H.; Knox, Lawrence H.; Murphy, James L.; Velarde, E.

doi:10.1021/ja01016a066

Cited by 14 publications

(2 citation statements)

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“…(4) Hydrolysis of 3,3-Difluoro-1-iodocyclopropenes. It is known that gem -difluorocyclopropenes are susceptible both to basic and acidic hydrolysis to afford the corresponding cyclopropanones regardless of whether an alkyl group or hydrogen is present on the cyclopropene ring. However, in our case, 4a and 4e were demonstrated to be completely inert under basic conditions, such as 50% aqueous sodium hydroxide in methanol, acetone, diglyme, or ether (Bu 4 NBr was added as a phase-transfer agent).…”

Section: Resultsmentioning

confidence: 99%

3,3-Difluoro-1-iodocyclopropenes: A Simple Synthesis and Their Reactions

Chen

2002

J. Org. Chem.

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The [1 + 2] cycloaddition reaction of 1-iodoalkynes with difluorocarbene, generated from the decomposition of FSO(2)CF(2)COOSiMe(3) in diglyme in the presence of 10 mol % NaF at 120 degrees C, gives 3,3-difluoro-1-iodocyclopropenes in good yields. These new iodides can be trifluoromethylated and functionalized via the Heck reaction. The unusual hydrolytic reactions of the iodides under acidic conditions was also investigated.

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Section: Resultsmentioning

confidence: 99%

3,3-Difluoro-1-iodocyclopropenes: A Simple Synthesis and Their Reactions

Chen

2002

J. Org. Chem.

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“…The formation of C is consistent with the synthesis of similar polyfluorinated bicyclobutane ring systems formed by CF 2 carbene addition to acetylenes. 8,9 Intermediate C then appears to undergo a [2+2] cycloaddition with a further equivalent of acetylene ether 3 to generate 5. This final event is consistent with the calculated low energy activation barrier for the central C-C bond cleavage in fluoro-bicyclobutanes.…”

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confidence: 99%