353302-31-5Relevant academic research and scientific papers
SYSTEMS AND METHODS FOR REGIOSELECTIVE CARBONYLATION OF 2,2-DISUBSTITUTED EPOXIDES
-
Paragraph 0088;0183, (2020/06/05)
Provided are methods of carbonylating cyclic substrates to produce carbonyl ated cyclic products. The cyclic substrates may be 2, 2-di substituted epoxides and the cyclic products may be β,β-di substituted lactones. The method may be carried out by forming and pressurizing a reaction mixture of the cyclic substrate, a solvent, carbon monoxide, and a [LA+][CO(CO)4-] catalyst, where [LA+] is a Lewis acid capable of coordinating to the cyclic substrate. The method may proceed with a regioselectivity of 90:10 or greater. The resulting carbonylated cyclic products may be converted to ketone aldol products that retain the stereochemistry and enantiomeric ratio of the carbonyl ated cyclic products.
Regioselective Carbonylation of 2,2-Disubstituted Epoxides: An Alternative Route to Ketone-Based Aldol Products
Hubbell, Aran K.,Lapointe, Anne M.,Lamb, Jessica R.,Coates, Geoffrey W.
supporting information, p. 2474 - 2480 (2019/02/14)
We report the regioselective carbonylation of 2,2-disubstituted epoxides to β,β-disubstituted β-lactones. Mechanistic studies revealed epoxide ring-opening as the turnover limiting step, an insight that facilitated the development of improved reaction conditions using weakly donating, ethereal solvents. A wide range of epoxides can be carbonylated to β-lactones, which are subsequently ring-opened to produce ketone-based aldol adducts, providing an alternative to the Mukaiyama aldol reaction. Enantiopure epoxides were demonstrated to undergo the carbonylation/ring-opening process with retention of stereochemistry to form enantiopure β-hydroxy esters.
C2-Symmetric Cu(II) Complexes as Chiral Lewis Acids. Catalytic, Enantioselective Cycloadditions of Silyl Ketenes
Evans, David A.,Janey, Jacob M.
, p. 2125 - 2128 (2007/10/03)
(matrix presented) C2-Symmetric bis(oxazoline)-Cu(II) complexes (4a-g) catalyze the enantioselective [2 + 2] cycloaddition between (silyl)ketenes and chelating carbonyl substrates. A range of substituted β-lactones can be produced in excellent yields and selectivities. It was also found that (trimethylsilyl)-ketene (1) may also undergo a highly selective hetero Diels-Alder reaction with β,γ-unsaturated α-keto esters.
