Abstract
The addition of various carboxylic acids to (trans -2-ethoxycyclopropyl)ethyne (1 ) by catalysis with [Ru(O2 CH)(CO)2 (PPh3 )]2 proceeds regioselectively in the Markovnikov sense with ring opening of the cyclopropyl
group to furnish allenylacetaldehyde acyl ethyl acetals 3 in high yields (44-96%, 11 examples). The allenylacetaldehyde derivatives undergo
palladium-catalyzed Heck-type cross coupling with iodobenzene and subsequent trapping
of the π-allylpalladium intermediate with primary and secondary amines to yield labile
[β-(1-aminomethyl)styryl]acetaldehyde acyl ethyl acetals 12 (24-83%, 4 examples). Anti-Markovnikov addition of carboxylic acids to the triple
bond in (trans -2-ethoxycyclopropyl)ethyne (1 ) without ring opening can be brought about under [Ru(CH2 CMeCH2 )2 (dppb)] catalysis to give 2-(trans -2-ethoxycyclopropyl)ethenyl esters 13 (69-92%, 3 examples). (1-Hydroxycyclopropyl)ethyne (14 ), under catalysis by [Ru(O2 CH)(CO)2 (PPh3 )]2 , reacts with carboxylic acids to yield 1-acetylcyclopropyl esters 15 (49-74%, 4 examples) by Markovnikov-sense addition and intramolecular transesterification.
Anti-Markovnikov- and Markovnikov-sense addition of carboxylic acids to unsubstituted
cyclopropylethyne can both be achieved regioselectively under catalysis with [Ru(CH2 CMeCH2 )2 (dppb)] and [Ru(O2 CH)(CO)2 (PPh3 )]2 to furnish 2-cyclopropylethenyl esters 23 (68-98%, 6 examples) and 1-cyclopropylethenyl esters 24 (66-97%, 5 examples), respectively.
Key words
acetylenes - cyclopropanes - allenes - ruthenium catalysis - palladium catalysis
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