77300-22-2Relevant articles and documents
Selective aliphatic carbon-hydrogen bond activation of protected alcohol substrates by cytochrome P450 enzymes
Bell, Stephen G.,Spence, Justin T. J.,Liu, Shenglan,George, Jonathan H.,Wong, Luet-Lok
, p. 2479 - 2488 (2014/04/03)
Protected cyclohexanol and cyclohex-2-enol substrates, containing benzyl ether and benzoate ester moieties, were designed to fit into the active site of the Tyr96Ala mutant of cytochrome P450cam. The protected cyclohexanol substrates were efficiently and selectively hydroxylated by the mutant enzyme at the trans C-H bond of C-4 on the cyclohexyl ring. The selectivity of oxidation of the benzoate ester protected cyclohexanol could be altered by making alternative amino acid substitutions in the P450cam active site. The addition of the double bond in the cyclohexyl ring of the benzoate ester protected cyclohex-2-enol has a debilitative effect on the activity of the Tyr96Ala mutant with this substrate. However, the Phe87Ala/Tyr96Phe double mutant, which introduces space at a different location in the active site than the Tyr96Ala mutant, was able to efficiently hydroxylate the C-H bonds of 1-cyclohex-2-enyl benzoate at the allylic C-4 position. Mutations at Phe87 improved the selectivity of the oxidation of 1-phenyl-1-cyclohexylethylene to trans-4-phenyl-ethenylcyclohexanol (92%) when compared to single mutants at Tyr96 of P450cam. the Partner Organisations 2014.
STEREOCHEMICAL STUDIES - LVII. SYNTHESIS OF OPTICALLY ACTIVE COMPOUNDS BY THE NOVEL USE OF MESO-COMPOUNDS -1. EFFICIENT SYNTHESIS OF TWO STRUCTURAL TYPES OF OPTICALLY PURE PROSTAGLANDIN INTERMEDIATES.
Nara, M,Terashima, S.,Yamada, S.
, p. 3161 - 3170 (2007/10/02)
With an aim to overcome several inefficient aspects of ordinary methods of preparing optically active compounds, we have developed a new method which recommends utilization of symmetrically functionalized meso-compounds in place of racemic compounds.As shown in Scheme 1, when the meso-compound (I) is monofunctionalized by an optically active functional group (A) and each of the formed diastereomers (II and III) is subjected to further chemical elaborations including protective group transposition, it is theoretically possible to convert the total amount of the starting material (I) into the requisite optically pure product (VI or VII) by selecting synthetic schemes.By employing this novel concept, two structural types of the prostaglandin intermediates ((-)- and (+)-2a,b) have been prepared from the meso-diols (1a,b) by way of the two diastereomeric monoesters (13a,b and 14a,b) which are produced by the reactions 1a,b with N-mesyl- and N-phthaloyl-(S)-phenylalanyl chloride (3a,b).
