1003-83-4Relevant articles and documents
Asymmetric microbial hydrolysis of epoxides
Mischitz,Kroutil,Wandel,Faber
, p. 1261 - 1272 (1995)
Kinetic resolution of 2-mono- and 2,2-disubstituted epoxides was accomplished using epoxide hydrolases from bacterial and fungal origin by employing lyophilized whole microbial cells. In all cases investigated, the biocatalytic hydrolysis was shown to proceed with retention of configuration at the stereogenic center leading to 1,2-diols and remaining epoxides. The selectivity of the reaction was dependent on the substrate structure and the strain used with E-values ranging from low or moderate (with 2-monosubstituted epoxides) to excellent (E >100, with 2,2-disubstituted oxiranes).
Mechanically Gated Degradable Polymers
Lin, Yangju,Kouznetsova, Tatiana B.,Craig, Stephen L.
, p. 2105 - 2109 (2020)
Degradable polymers are desirable for the replacement of conventional organic polymers that persist in the environment, but they often suffer from the unintentional scission of the degradable functionalities on the polymer backbone, which diminishes polymer properties during storage and regular use. Herein, we report a strategy that combats unintended degradation in polymers by combining two common degradation stimuli - mechanical and acid triggers - in an "AND gate" fashion. A cyclobutane (CB) mechanophore is used as a mechanical gate to regulate an acid-sensitive ketal that has been widely employed in acid degradable polymers. This gated ketal is further incorporated into the polymer backbone. In the presence of an acid trigger alone, the pristine polymer retains its backbone integrity, and delivering high mechanical forces alone by ultrasonication degrades the polymer to an apparent limiting molecular weight of 28 kDa. The sequential treatment of ultrasonication followed by acid, however, leads to a further 11-fold decrease in molecular weight to 2.5 kDa. Experimental and computational evidence further indicate that the ungated ketal possesses mechanical strength that is commensurate with the conventional polymer backbones. Single molecule force spectroscopy (SMFS) reveals that the force necessary to activate the CB molecular gate on the time scale of 100 ms is approximately 2 nN.
The synthesis of the 2, 3-difluorobutan-1, 4-diol diastereomers
Szpera, Robert,Kovalenko, Nadia,Natarajan, Kalaiselvi,Paillard, Nina,Linclau, Bruno
, p. 2883 - 2887 (2017)
The diastereoselective synthesis of fluorinated building blocks that contain chiral fluorine substituents is of interest. Here we describe optimisation efforts in the synthesis of anti-2, 3-difluorobutane-1, 4-diol, as well as the synthesis of the corresponding syn-diastereomer. Both targets were synthesised using an epoxide opening strategy.
Preparation process method of gadobutrol epoxy side chain intermediate
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Paragraph 0070-0079; 0090-0098; 0129-0136, (2017/08/29)
The invention disclose a 4,4-dimethyl 3,5,8-trioxabic [5,1,0]ycloctane and particularly relates to a preparation process method of a gadobutrol epoxy side chain intermediate. According to the preparation process method disclosed by the invention, by adjusting the weight ratio of feeding materials, optimizing reaction conditions and improving post treatment and purification methods, the impurity content of an obtained gadobutrol epoxy side chain intermediate product is low; the quality of the intermediate product is greatly improved while the yield is increased, so that the difficulty of process control of the gadobutrol crude drugs during the production process is reduced, and the quality and the qualification rate of the gadobutrol crude drugs are improved. The preparation process method disclosed by the invention has the advantages of simple operation methods in all process steps, safe and feasible solvent and technological conditions, realization of green and environmental-friendly production and wide application prospect.
Further synthetic attempts towards calicene
Al-Dulayymi, Ahmad,Li, Xiaoming,Neuenschwander, Markus
, p. 1633 - 1644 (2007/10/03)
First synthetic attempts towards the so-far-unknown calicene (= 5- (cycloprop-2-en-1-ylidene)cyclopenta-1,3-diene) precursors 3-(cyclopenta-2,4- dien-1-ylidene)tricyclo[3.2.2.22.4]nona-6,8-diene (4; Scheme 1), 1,4- di(cyclopenta-2,4-dien-1-ylid