Control of stereoselectivity of benzylic hydroxylation catalysed by wild-type cytochrome P450BM3 using decoy molecules

Control of stereoselectivity of benzylic hydroxylation catalysed by wild-type cytochrome P450BM3 using decoy molecules

Catal. Sci. Technol., 2017, Advance Article
DOI: 10.1039/C7CY01130J, Paper
Kazuto Suzuki, Joshua Kyle Stanfield, Osami Shoji, Sota Yanagisawa, Hiroshi Sugimoto, Yoshitsugu Shiro, Yoshihito Watanabe
The benzylic hydroxylation of non-native substrates was catalysed by cytochrome P450BM3, wherein “decoy molecules” controlled the stereoselectivity of the reactions.
  • Catalysis Science & Technology

Control of stereoselectivity of benzylic hydroxylation catalysed by wild-type cytochrome P450BM3 using decoy molecules

Abstract

The hydroxylation of non-native substrates catalysed by wild-type P450BM3 is reported, wherein “decoy molecules”, i.e., native substrate mimics, controlled the stereoselectivity of hydroxylation reactions. We employed decoy molecules with diverse structures, resulting in either a significant improvement in enantioselectivity or clear inversion of stereoselectivity in the benzylic hydroxylation of alkylbenzenes and cycloalkylbenzenes. For example, supplementation of wild-type P450BM3 with 5-cyclohexylvaleric acid-L-phenylalanine (5CHVA-Phe) and Z-proline-L-phenylalanine yielded 53% (R) ee and 56% (S) ee for indane hydroxylation, respectively, although 16% (S) ee was still observed in the absence of any additives. Moreover, we performed a successful crystal structure analysis of 5CHVA-L-tryptophan-bound P450BM3 at 2.00 Å, which suggests that the changes in selectivity observed were caused by conformational changes in the enzyme induced by binding of the decoy molecules.

M2 Kazuto Suzuki \ suzuki.kazuto*c.mbox.nagoya-u.ac.jp

Yoshihito Watanabe yoshi*nucc.cc.nagoya-u.ac.jp

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Atom- and step-economical nucleophilic arylation of azaaromatics via electrochemical oxidative cross C-C coupling reactions

Green Chemistry International

Atom- and step-economical nucleophilic arylation of azaaromatics via electrochemical oxidative cross C-C coupling reactions

Green Chem., 2017, 19,2931-2935
DOI: 10.1039/C7GC00789B, Communication
O. N. Chupakhin, A. V. Shchepochkin, V. N. Charushin
A simple and efficient electrochemical method for the synthesis of asymmetrical bi(het)aryls through direct functionalization of the C(sp2)-H bond in azaaromatics with fragments of (hetero)aromatic nucleophiles has been developed

From the journal:

Green Chemistry

Atom- and step-economical nucleophilic arylation of azaaromatics via electrochemical oxidative cross C–C coupling reactions

Abstract

The synthesis of asymmetrical bi(het)aryls through direct functionalization of the C(sp2)–H…

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