01671nas a2200169   4500008004100000022001400041245015500055210006900210260000800279300001400287490000700301520099700308100002101305700002301326700002401349856012801373       2025                        eng d  a1523-706000aNHC-catalyzed allylation of aldehydes with MBH carbonates and their michael addition-elimination-cope rearrangement cascade: a route to rac-sacubitril0 aNHCcatalyzed allylation of aldehydes with MBH carbonates and the  cMAY  a5911-59160 v273 a<p>
	We report herein a novel NHC-catalyzed transition-metal-free chemoselective allylation of aldehydes with Morita-Baylis-Hillman (MBH) carbonates using an inorganic base. Fascinatingly, the use of an organic base follows a different mechanism, leading to highly functionalized 1,5-dienes via a Michael addition-elimination reaction followed by [3,3]-sigmatropic Cope rearrangement. The described method harnesses a new Csp2-Csp3 bond to access alpha-methylene-gamma-oxo-gamma-substituted ester derivatives paving a way to facile synthesis of potent natural products and active pharmaceutical ingredients (APIs). A broad range of aromatic and aliphatic aldehydes with MBH carbonates was employed to provide a variety of interesting butanoate and dienyl ketone scaffolds in good to excellent yields. This chemistry has been extended to the efficient syntheses of rac-sacubitril API and gamma-butyrolactone scaffold, which is a privileged core present in many natural products and APIs</p>
1 aKale, Tushar, B.1 aJagtap, Sayali, G.1 aMhaske, Santosh, B.  uhttps://library.ncl.res.in/content/nhc-catalyzed-allylation-aldehydes-mbh-carbonates-and-their-michael-addition-elimination