Asymmetric organic carbonate synthesis catalyzed by an enzyme with dimethyl carbonate: a fruitful sustainable alliance

Acid-catalysed carboxymethylation, methylation and dehydration of alcohols and phenols with dimethyl carbonate under mild conditions

“…19 Beyond base catalysis, the ionic liquid 1-(3-trimethoxysilylpropyl)-3-methylimidazolium chloride was found to be an activated reaction medium for the synthesis of non-symmetrical dialkyl carbonates, 20 while enzymatic carboxymethylation of alcohols has also been reported. 21 However, there is very limited literature on acid catalysed (Brønsted or Lewis acid) carboxymethylation or methylation of aliphatic alcohols/phenolic compounds with DMC.…”

Lipase-mediated flow synthesis of nature-inspired phenolic carbonates

“…First, the chemoselective carbomethoxylation of the alcoholic function of Ty and HTy was performed under ow conditions using a cheap, non-toxic and green carboxymethylating agent as dimethyl carbonate (DMC), 26,27 exploited also as reaction medium, and Novozyme 435® as biocatalyst (imm-CaLB). 28,29 The carbomethoxylation reaction usually relies on the use of organocatalyst under heating 30,31 and, until now, the synthesis of compounds 1 and 2 has been achieved mainly using an acidic catalyst under prolonged heating. [32][33][34] The immobilized biocatalyst was packed into a glass reactor column and a solution of Ty in DMC was owed through it (Table 1); temperature (T, range: 40-80 °C), Ty concentration (C Ty , range: 100-250 mM), and residence time (R t , range: 5-15 min) were varied and conversion (c) was evaluated by HPLC (Table 1).…”

Intensification of Double Kinetic Resolution of Chiral Amines and Alcohols via Chemoselective Formation of a Carbonate–Enzyme Intermediate

“…The analysis of model reaction products showed that the enzyme is not only chemoselective towards mixed carbonate, but also highly enantioselective. Among the previously published protocols regarding enzymatic synthesis of mixed carbonates, enantioselectivity was neither analyzed nor optimized [ 19 ]. To fill this gap, the optimization of reaction conditions was performed ( Supplementary Materials , Section: Enzymatic kinetic resolution of alcohols).…”

“…Notably, alcohol (R)-1h was synthesized with a high yield and >99% ee, which is very difficult to obtain using acyl donors such as vinyl acetate [22]. The compound 1h was recognized as a synthon of substances such as δ-lactones [37], inhibitors of soluble epoxide hydrolase [38], and FICA (novel derivatives used for determining the absolute configuration of secondary alcohols using 19 F and 1 H NMR spectroscopy) [39].…”