The first Lewis base-catalysed chemoselective asymmetric N-allylic alkylation of enamides with Morita-Baylis-Hillman carbonates has been developed, which affords multifunctional products in moderate to high enantioselectivity (up to 92% ee).

Conscious of the importance that stereochemical issues may have on the design of efficient organocatalyts for both Morita-Baylis-Hillman and aza-Morita-Baylis-Hillman reaction we have analyzed them in this minireview. The so-called standard reactions involve "naked" enolates which therefore should lead to the syn adducts as the major products, irrespective of the E, Z stereochemistry of the eno...

Brucine diol (BD) catalyzed asymmetric Morita–Baylis–Hillman (MBH) reaction is observed for the first time. N-oxide (BNO) was found to not have an effective chiral catalyst. Faster rate obtained using unsaturated ester or aromatic aldehydes in presence of BNO. 4-Nitrobenzaldehyde and α,β-unsaturated ketone/ester were converted MBH adduct moderate yields (up 74%) with 70% ee value by this cataly...

Silica gel was found to be an excellent medium for some useful organic transformations under organic solvent-free conditions, such as (1) the Friedel-Crafts-type nitration of arenes using commercial aqueous 69% nitric acid alone at room temperature, (2) one-pot Wittig-type olefination of aldehydes with activated organic halides in the presence of tributyl- or triphenylphosphine and Hunig's base...

Herein we report the metal-free diastereoselective frustrated Lewis pair (FLP)-catalyzed hydrogenation of azaMorita−Baylis−Hillman (aza-MBH) adducts, accessing a diverse range of stereodefined β-amino acid derivatives in excellent isolated yields (28 examples, 89% average yield, up to 90:10 d.r.). Furthermore, sequential organo-FLP catalysis has been developed. An initial organocatalyzed aza-MB...

The title compound, C18H17NO5, was prepared by a synthetic strategy based on the Heck reaction from Morita-Baylis-Hillman adducts. The five-membered ring adopts a slightly twisted conformation on the Ca-Cm (a = aromatic and m = methyl-ene) bond. The dihedral angle between the five-membered ring and the spiro aromatic ring is 89.35 (7)°; that between the five-membered ring and the 4-meth-oxy-ben...

Reaction of nitroalkenes or nitrodienes with methyl vinyl ketone (MVK) or acrylate in the presence of the imidazole-LiCl catalyst system provides Rauhut-Currier (vinylogous Morita-Baylis-Hillman) adducts in moderate yield. Under similar conditions (imidazole-hydroquinone), nitroalkenes and nitrodienes undergo self-dimerization to afford the Rauhut-Currier adducts in varying yields. An alternati...

Significance: This paper describes the palladiumcatalyzed enantioselective aza-Morita–Baylis–Hillman reaction of acrylonitriles with imines. The bulky pincer ligand enabled the synthesis of enantioenriched α-methylene-β-aminonitriles in high yield. Comment: The palladium–pincer complex preferably activates acrylonitrile, even in the presence of ethyl acrylate. The palladium ketenimide is a key ...