A formal enantioselective synthesis of benazepril.HCl (4), an anti- hypertensive drug, is reported. Our synthesis employed an asymmetric aza-Michael addition of L-homophenylalanine ethyl ester (LHPE, 1) to 4-(2-nitrophenyl)-4-oxo- but-2-enoic acid methyl ester (6) as the key step to prepare (2S,3'S)-2-(2-oxo-2,3,4,5- tetrahydro-1H-benzo[b]azepin-3-ylamino)-4-phenylbutyric acid ethyl ester (8), ...

Several transition metal salts were found to catalyze aza-Michael reactions of enones with carbamates efficiently. The catalytic activity was strongly dependent on the nature of the metal salts. While conventional Lewis acids such as BF(3).OEt(2), AlCl(3), or TiCl(4) showed lower activity, group 7-11 transition metal salts in higher oxidation states such as ReCl(5), Fe(ClO(4))(3).9H(2)O, RuCl(3...

A highly efficient phase-transfer catalytic aza-Michael addition of tert-butyl benzyloxycarbamate to a wide range of electron-deficient olefins is presented (90-99%).

Correction to:Sequencing Groebke–Blackburn–Bienaymé and Aza-Michael Addition Reactions: A Modular Strategy for Accessing a Diverse Collection of Constrained Benzoxazepine Imidazopyrazine SystemsSynthesis 2021; 53(11): 1911-1922DOI: 10.1055/s-0040-1706006

A concise total synthesis of mesembrine (four steps from known compound) was achieved both racemically and asymmetrically. Two key reactions were used here. One is the Rh(I)-catalyzed [5 + 1] cycloaddition of vinylcyclopropane 3c and CO. The other one is Buchwald's Pd-catalyzed coupling reaction that coupled β,γ-cyclohexenone 2c with aryl bromide 5 (using dppe ligand for racemic or (S)-Antphos ...