58046-75-6Relevant academic research and scientific papers
The intramolecular Morita-Baylis-Hillman-type alkylation reaction
Cran, John W.,Krafft, Marie E.,Seibert, Kimberly A.,Haxell, Thomas F.N.,Wright, James A.,Hirosawa, Chitaru,Abboud, Khalil A.
experimental part, p. 9922 - 9943 (2012/02/05)
From the initial development of a homologous Morita-Baylis-Hillman reaction utilizing epoxides as electrophiles, the method was expanded to enable the exclusively organocatalyzed intramolecular allylation of enones and to develop the intramolecular MBH-type alkylation of activated alkenes. We successfully utilized both enones and unsaturated thioesters as the activated alkene component. This work, carried out using stoichiometric amounts of the trialkylphosphine, gave an array of functionalized five- and six-membered carbocycles in high yields. With the cycloalkylation of enones and thioesters, conditions that allowed the use of substoichometric amounts of the phosphine catalyst were developed. As a result both five- and six-membered rings can be formed efficiently with little to no loss in yield upon comparison to yields obtained when stoichiometric amounts of trialkylphosphines were employed. We isolated, for the first time, an MBH-type intermediate exhibiting unprecedented trans geometry of the phosphonium salt and acyl group.
New directions for the Morita-Baylis-Hillman reaction; homologous aldol adducts via epoxide opening
Krafft, Marie E.,Wright, James A.
, p. 2977 - 2979 (2008/09/19)
Under trialkylphosphine catalyzed Morita-Baylis-Hillman reaction conditions, epoxides react with enones to give rise to homologous aldol adducts. The Royal Society of Chemistry 2006.
Anomalous 5-endo-trig reversals: general reactions of 7-oxabicycloheptenes and heptanes
Keay, B. A.,Rajapaksa, D,Rodrigo, R.
, p. 1093 - 1098 (2007/10/02)
Two general reversals of 7-oxabicycloheptanes are described and discussed.The reverse-Michael reaction occurs with the aldehyde, ketone, ester, and nitrile derivatives while the reverse aldol readtion catalysed by acid is confined to the aldehydes and ketones.The properties of the title compounds are rationalized in terms of the geometric alignments of the bonding and antibonding orbitals of the bridging oxygen atom and its neighboring carbons.New isobenzofuran and cyclohexadiene syntheses form a part of the report.
