Enzymatic Desymmetrising Redox Reactions for the Asymmetric Synthesis of Biaryl Atropisomers

Samantha Staniland; Bo Yuan; Nelson Giménez-Agullõ; Tommaso Marcelli; Simon C. Willies; Damian M. Grainger; Nicholas J. Turner; Jonathan Clayden

doi:10.1002/chem.201404509

Enzymatic Desymmetrising Redox Reactions for the Asymmetric Synthesis of Biaryl Atropisomers

Samantha Staniland, Bo Yuan, Nelson Giménez-Agullõ, Tommaso Marcelli, Simon C. Willies, Damian M. Grainger, Nicholas J. Turner^*, Jonathan Clayden

^*Corresponding author for this work

School of Chemistry

Research output: Contribution to journal › Article (Academic Journal) › peer-review

23 Citations (Scopus)

Abstract

Atropisomeric biaryls carrying ortho-hydroxymethyl and formyl groups were made enantioselectively by desymmetrisation of dialdehyde or diol substrates. The oxidation of the symmetrical diol substrates was achieved using a variant of galactose oxidase (GOase), and the reduction of the dialdehydes using a panel of ketoreductases. Either M or P enantiomers of the products could be formed, with absolute configurations assigned by time-dependent DFT calculations of circular dichroism spectra. The differing selectivities observed with different biaryl structures offer an insight into the detailed structure of the active site of the GOase enzyme.

Original language	English
Pages (from-to)	13084-13088
Number of pages	5
Journal	Chemistry - A European Journal
Volume	20
Issue number	41
Early online date	22 Aug 2014
DOIs	https://doi.org/10.1002/chem.201404509
Publication status	Published - 6 Oct 2014

Keywords

atropisomerism
biaryls
biocatalysis
galactose oxidase
ketoreductase

Access to Document

10.1002/chem.201404509

Cite this

@article{0dbc9f5a40954beeb0ed0a01394f012d,

title = "Enzymatic Desymmetrising Redox Reactions for the Asymmetric Synthesis of Biaryl Atropisomers",

abstract = "Atropisomeric biaryls carrying ortho-hydroxymethyl and formyl groups were made enantioselectively by desymmetrisation of dialdehyde or diol substrates. The oxidation of the symmetrical diol substrates was achieved using a variant of galactose oxidase (GOase), and the reduction of the dialdehydes using a panel of ketoreductases. Either M or P enantiomers of the products could be formed, with absolute configurations assigned by time-dependent DFT calculations of circular dichroism spectra. The differing selectivities observed with different biaryl structures offer an insight into the detailed structure of the active site of the GOase enzyme.",

keywords = "atropisomerism, biaryls, biocatalysis, galactose oxidase, ketoreductase",

author = "Samantha Staniland and Bo Yuan and Nelson Gim{\'e}nez-Agull{\~o} and Tommaso Marcelli and Willies, {Simon C.} and Grainger, {Damian M.} and Turner, {Nicholas J.} and Jonathan Clayden",

year = "2014",

month = oct,

day = "6",

doi = "10.1002/chem.201404509",

language = "English",

volume = "20",

pages = "13084--13088",

journal = "Chemistry - A European Journal",

issn = "0947-6539",

publisher = "Wiley-VCH Verlag",

number = "41",

}

Enzymatic Desymmetrising Redox Reactions for the Asymmetric Synthesis of Biaryl Atropisomers. / Staniland, Samantha; Yuan, Bo; Giménez-Agullõ, Nelson; Marcelli, Tommaso; Willies, Simon C.; Grainger, Damian M.; Turner, Nicholas J.; Clayden, Jonathan.

In: Chemistry - A European Journal, Vol. 20, No. 41, 06.10.2014, p. 13084-13088.

Research output: Contribution to journal › Article (Academic Journal) › peer-review

TY - JOUR

T1 - Enzymatic Desymmetrising Redox Reactions for the Asymmetric Synthesis of Biaryl Atropisomers

AU - Staniland, Samantha

AU - Yuan, Bo

AU - Giménez-Agullõ, Nelson

AU - Marcelli, Tommaso

AU - Willies, Simon C.

AU - Grainger, Damian M.

AU - Turner, Nicholas J.

AU - Clayden, Jonathan

PY - 2014/10/6

Y1 - 2014/10/6

N2 - Atropisomeric biaryls carrying ortho-hydroxymethyl and formyl groups were made enantioselectively by desymmetrisation of dialdehyde or diol substrates. The oxidation of the symmetrical diol substrates was achieved using a variant of galactose oxidase (GOase), and the reduction of the dialdehydes using a panel of ketoreductases. Either M or P enantiomers of the products could be formed, with absolute configurations assigned by time-dependent DFT calculations of circular dichroism spectra. The differing selectivities observed with different biaryl structures offer an insight into the detailed structure of the active site of the GOase enzyme.

AB - Atropisomeric biaryls carrying ortho-hydroxymethyl and formyl groups were made enantioselectively by desymmetrisation of dialdehyde or diol substrates. The oxidation of the symmetrical diol substrates was achieved using a variant of galactose oxidase (GOase), and the reduction of the dialdehydes using a panel of ketoreductases. Either M or P enantiomers of the products could be formed, with absolute configurations assigned by time-dependent DFT calculations of circular dichroism spectra. The differing selectivities observed with different biaryl structures offer an insight into the detailed structure of the active site of the GOase enzyme.

KW - atropisomerism

KW - biaryls

KW - biocatalysis

KW - galactose oxidase

KW - ketoreductase

UR - http://www.scopus.com/inward/record.url?scp=84941029578&partnerID=8YFLogxK

U2 - 10.1002/chem.201404509

DO - 10.1002/chem.201404509

M3 - Article (Academic Journal)

C2 - 25156181

AN - SCOPUS:84941029578

VL - 20

SP - 13084

EP - 13088

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

SN - 0947-6539

IS - 41

ER -

Enzymatic Desymmetrising Redox Reactions for the Asymmetric Synthesis of Biaryl Atropisomers

Abstract

Keywords

Access to Document

Other files and links

Fingerprint

Cite this