Acetophenone, methyl acrylate

Riant et al. in 2006 reported an enantioselective reductive aldol reaction of acetophenone and methyl acrylate mediated by PhSiH3 (140 mol %) and catalyzed by a complex generated in situ from [CuF(Ph3P)3]2MeOH (1-3 mol %) and a chiral bisphosphine (1-3 mol %) [57]. According to Mori s... 

In one of the few examples of a chiral ligand-controlled asymmetric reaction mediated by Sml2, Mikami reported the use of the chiral, bis-phosphine oxide, BINAPO (4), as a Lewis basic additive.23 For example, reductive coupling of methyl acrylate and acetophenone using Sml2 in THF with 2 equiv of BINAPO gave lactone 5 in 46% yield and 67% ee (Scheme 2.8).23... 

Methyl acrylate (37) was used as a reagent for annulation with the phenyl imine derivative of acetophenone. For example, phenyl imine 78 was converted to 79 by treatment with 37 in the presence of AICI3 (eq. 20).34 The enamine formed from acetophenone (80) and NH4OAC was converted to 82 by combination with 81 (eq. 21).17 In the case of 81, the aryl substituent provided a steric and electronic hindrance to the aza-annulation reaction, but the reactivity of the reagent was enhanced by the combined effects of the C02Et and CN functionality. Due to the nature of the substituents on the intermediate dihydropyridone, dehydrogenation occurred to form pyridone 82. 

Recently, enantioselective additions of samarium diiodide-generated ketyl radicals to olefins have been demonstrated [15]. As illustrated in Eq. (10), the reductive coupling of acetophenone with methyl acrylate (31a) in the presence of chiral phosphine ligand 29 (i -BINAPO) gives somewhat low yields (mostly under 50%) but moderate to good levels of enantioselectivity (60-70% ee) for the y-butyrolactone products 34. 

BzA was polymerized in a higher yield than BA, in spite of the greater bulkiness of the benzyl group. This seems to be the result of a high affinity of the aromatic group to poly(NMAAm), which causes BzA monomer to proceed easily to an active center. Poly(NMAAm) swells considerably in aromatic solvents such as benzene, acetophenone and methyl benzoate, but not in the aliphatics such as acetone, acetonitrile and AcOEt. However, the block copolymer yield in the BzA system was lower than with other acrylates. This is attributed to the participation of labile benzylic hydrogen of BzA in chain transfer reactions. 

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