BiCl₃-Facilitated removal of methoxymethyl-ether/ester derivatives and DFT study of –O–C–O– bond cleavage

Abstract

A simple method for cleavage of methoxymethyl (MOM)-ether and ester derivatives using bismuth trichloride (BiCl3) is described. Alkyl, alkenyl, alkynyl, benzyl and anthracene MOM ether derivatives as well as MOM...

Decoding the reaction mechanism of the cyclocondensation of ethyl acetate2‐oxo‐2‐(4‐oxo‐4H‐pyrido [1.2‐a] pyrimidin‐3‐yl) polyazaheterocycle and ethylenediamine using bond evolution theory

“…The cyclisation via TS1‐b is the most polar one, in clear agreement with the mechanism. These GEDT values suggest a polar character of this cyclocondensation reaction according to Domingo who proposed that reactions with GEDT values of 0.0 |e| as non‐polar processes, while those with values higher than 0.2 |e| correspond to polar processes 30 . This result is in clear agreement with the analysis of the CDFT indices at the ground state of the reactants.…”

“…In view of the above and in continuation with our interest to study reaction mechanism, 30 in this work, we carried out the BET study of the mechanism of cyclocondensation reaction of ethyl acetate 2‐oxo‐2‐(4‐oxo‐4 H ‐pyrido[1.2‐a]pyrimidin‐3‐yl) acetate polyazaheterocycle ( 1 ) and ethylenediamine ( 2 ) (Scheme 1). In particular, this study provides a detailed understanding of the chemical reactivity of cyclocondensation reaction of polyazaheterocycle ( 1 ) with ( 2 ).…”

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

“…The following supporting information can be downloaded at: , General procedures; 1 H- and 13 CNMR spectra of the obtained products, carbonates and carbamates, GC and HPLC traces of the obtained products; Table S1: Optimal carbonate to alcohol ratio for EKR of alcohols performed on model substrates in MTBE; Table S2: Solvent screening for EKR of alcohols for model substrates; Table S3: Enantioselectivity studies of EKR of alcohols using carbonates; Table S4: E -values for scope limitation reactions; Table S5: Solvent screening for DEKR by carbonate alcoholysis; Table S6: Temperature optimization for DEKR by carbonate alcoholysis; Table S7: Solvent screening for DEKR by carbonate aminolysis; Table S8: Temperature optimization for DEKR by carbonate aminolysis; Table S9: Enzyme recyclability studies; Table S10: E -values for scope limitation reactions of DEKR, with 1o serving as acyl acceptor; Table S11: Recovery yield studies for model DEKR reaction, Table S12: E -values for scope limitation reactions of DEKR, with 1p serving as acyl acceptor; Table S13: Upscale studies for selected reactions; Table S14: Upscale studies for selected DEKR reactions by carbonate aminolysis, Figure S1: Time course for model reaction of carbonate synthesis; Figure S2: Enzyme amount optimization for DEKR by carbonate alcoholysis; Figure S3: Time course of model DEKR by carbonate alcoholysis under optimized conditions Figure S4: Temperature optimization for model DEKR by aminolysis; Figure S5: Enzyme amount optimization for DEKR by aminolysis; Figure S6: Time course of model reaction in optimized conditions for DEKR by aminolysis. References [ 39 , 40 , 41 , 42 , 43 , 44 , 45 , 46 , 47 , 48 , 49 , 50 , 51 , 52 , 53 , 54 , 55 , 56 , 57 , 58 , 59 , 60 , 61 , 62 , 63 , 64 , 65 , 66 , 67 , 68 , 69 ,…”