Morita activated olefins

Ciganek E. The catalyzed a-hydroxylation and a-aminoalkylation of activated olefins (The Morita-BayUs-Hillman reaction). Org. Reactions 1997 51 201. 

The Catalyzed a-Hydroxylation and a-Aminoalkylation of Activated Olefins (The Morita-Baylis-Hillman Reaction) Engelbert Ciganek... 

The Wang group also realized enantioselective oxidative cross-coupling reactions between tertiary amines and the activated olefins by merging Cu(OTf)2 with quinine as the best cooperative catalysts/ A Morita-Baylis-Hillman-type mechanism is in operation. It was notable that molecular oxygen was employed as the sole oxidant. As shown in Scheme 2.12, the reactions between Ai-aryl THIQs and the a,p-unsaturated aldehydes or ketones 30 proceeded smoothly to afford the a-functionalized products 31 in up to 81% yield and 99% ee. 

During the past 40 years, the Morita-Baylis-Hillman reaction has seen exponential growth in terms of three components, that is, the activated olefins. 

It is well known that the Morita-Baylis-Hillman reaction originated from the phosphine-catalyzed dimerization of activated olefins reported by Rauhut and... 

During their studies on the design and synthesis of peptide mimetics, Ber-tenshaw and Kahn reported a three-component phosphine-catalyzed MBH reaction of activated olefins, aldehydes and amines, which provided a facile synthesis of 2-methylidene-3-aminopropanoates 190 based on the work of Morita (Scheme 2.94). ... 

In the same area, these authors have also investigated the efficiency of various chiral sterically congested phosphane-amide bifunctional organocatalysts with a binaphthyl scaffold in asymmetric aza-Morita-Baylis-Hillman reactions of A -sulfonated imines with activated olefins such as methyl and ethyl vinyl ketones." The corresponding aza-Morita-Baylis-Hillman adducts could be obtained in moderate to excellent yields (37-98%) and moderate to good... 

A review of the Morita-Baylis-Hillman (MBH) reaction has covered mechanism, activated olefins and electrophiles as substrates, multicomponent and intramolecular reactions, and the use of ionic liquid reaction media. ... 

Carbon-carbon bond forming reactions constitute die core of organic synthesis, and novel, efficient methods are always desirable. One such reaction that has attracted much attention in recent days is the Morita-Baylis-Hillman (MBH) reaction the reaction of activated olefins with reactive carbonyls or imines in the presence of a catalytic amount of trialkyl(aryl)phosphine or amine (i-i). Of all the amines tested, 1,4-diazabicyclo[2.2.2]octane (Dabco) has been found to be superior (Scheme 1). This reaction, which provides multifunctional molecules has been accommodated in certain undergraduate curriculum (4), and does not demand any sophisticated techniques or instrumentation. 

The first reactor-type thermoplastic polyolefin (R-TPO) was LLDPE/PP [Yamazaki and Eujimaki, 1970, 1972]. The three-component R-TPO s (PE with PP and EPR) soon followed [Strametz et al, 1975]. PE was also polymerized in the presence of active catalyst and an olefinic copolymer [Morita and Kashiwa, 1981]. Blending amorphous co-polyolefins with crystalline PO s (HDPE, LLDPE, PP), and a filler resulted in moldable blends, characterized by excellent sets of properties [Davis and Valaitis, 1993, 1994]. Blends of polycycloolefin (PCO) with a block copolymer (both polymerized in metallocene catalyzed process) and PE, were reported to show outstanding properties, viz. strength, modulus, heat resistance and toughness [Epple and Brekner, 1994]. 

The Morita-Baylis-Hillman reaction of imines with ynones in the presence of iodotrimethylsilane was efficiently catalyzed by ZrCU (Equation 15) [20]. Compared with the other Lewis acids, ZrCU showed much higher activity for the reaction. The newly formed olefin moiety has (E) configuration exclusively. 

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