Biocatalytic Conversion of Cyclic Ketones Bearing α-Quaternary Stereocenters into Lactones in an Enantioselective Radical Approach to Medium-Sized Carbocycles

Charlotte Morrill; Chantel N Jensen; Xavier Just-Baringo; Gideon Grogan; Nicholas Turner; David John Procter

doi:10.1002/anie.201800121

Biocatalytic Conversion of Cyclic Ketones Bearing α-Quaternary Stereocenters into Lactones in an Enantioselective Radical Approach to Medium-Sized Carbocycles

Charlotte Morrill, Chantel N Jensen, Xavier Just-Baringo, Gideon Grogan, Nicholas Turner, David John Procter

Chemistry

Research output: Contribution to journal › Article › peer-review

Abstract

Cyclic ketones bearing alpha-quaternary stereocenters undergo efficient kinetic resolution using cyclohexanone monooxygenase (CHMO) from Acinetobacter calcoaceticus. Lactones possessing tetrasubstituted stereocenters are obtained with high enantioselectivity (up to >99% ee) and complete chemoselectivity. Preparative scale biotransformations were exploited in conjunction with a SmI2-mediated cyclization process to access complex, enantiomerically enriched cycloheptan- and cycloctan-1,4-diols. In a parallel approach to structurally distinct products, enantioenriched ketones from the resolution bearing an alpha- all carbon quaternary stereocenter were used in a SmI2-mediated cyclization process to give cyclobutanol products (up to >99% ee).

Original language	English
Pages (from-to)	3692-3696
Number of pages	5
Journal	Angewandte Chemie International Edition
Volume	57
Issue number	14
Early online date	5 Mar 2018
DOIs	https://doi.org/10.1002/anie.201800121
Publication status	Published - 26 Mar 2018

Bibliographical note

Keywords

Journal Article

Access to Document

10.1002/anie.201800121

Morrill_et_al-2018-Angewandte_Chemie_International_Edition
© 2018 Wiley-VCH Verlag GmbH & Co. This is an author-produced version of the published paper. Uploaded in accordance with the publisher’s self-archiving policy. Further copying may not be permitted; contact the publisher for details
Accepted author manuscript, 1.87 MB
Morrill_et_al-2018-Angewandte_Chemie_International_Edition
© 2018 The Authors.
Final published version, 1.27 MBLicence: CC BY

Cite this

@article{74ad85d800f44feaae1576dc2302898a,

title = "Biocatalytic Conversion of Cyclic Ketones Bearing α-Quaternary Stereocenters into Lactones in an Enantioselective Radical Approach to Medium-Sized Carbocycles",

abstract = "Cyclic ketones bearing alpha-quaternary stereocenters undergo efficient kinetic resolution using cyclohexanone monooxygenase (CHMO) from Acinetobacter calcoaceticus. Lactones possessing tetrasubstituted stereocenters are obtained with high enantioselectivity (up to >99% ee) and complete chemoselectivity. Preparative scale biotransformations were exploited in conjunction with a SmI2-mediated cyclization process to access complex, enantiomerically enriched cycloheptan- and cycloctan-1,4-diols. In a parallel approach to structurally distinct products, enantioenriched ketones from the resolution bearing an alpha- all carbon quaternary stereocenter were used in a SmI2-mediated cyclization process to give cyclobutanol products (up to >99% ee).",

keywords = "Journal Article",

author = "Charlotte Morrill and Jensen, {Chantel N} and Xavier Just-Baringo and Gideon Grogan and Nicholas Turner and Procter, {David John}",

note = "{\textcopyright} 2018 The Authors.",

year = "2018",

month = mar,

day = "26",

doi = "10.1002/anie.201800121",

language = "English",

volume = "57",

pages = "3692--3696",

journal = "Angewandte Chemie International Edition",

issn = "1433-7851",

publisher = "Wiley-Blackwell",

number = "14",

}

Biocatalytic Conversion of Cyclic Ketones Bearing α-Quaternary Stereocenters into Lactones in an Enantioselective Radical Approach to Medium-Sized Carbocycles. / Morrill, Charlotte; Jensen, Chantel N; Just-Baringo, Xavier et al.

In: Angewandte Chemie International Edition, Vol. 57, No. 14, 26.03.2018, p. 3692-3696.

Research output: Contribution to journal › Article › peer-review

TY - JOUR

T1 - Biocatalytic Conversion of Cyclic Ketones Bearing α-Quaternary Stereocenters into Lactones in an Enantioselective Radical Approach to Medium-Sized Carbocycles

AU - Morrill, Charlotte

AU - Jensen, Chantel N

AU - Just-Baringo, Xavier

AU - Grogan, Gideon

AU - Turner, Nicholas

AU - Procter, David John

PY - 2018/3/26

Y1 - 2018/3/26

N2 - Cyclic ketones bearing alpha-quaternary stereocenters undergo efficient kinetic resolution using cyclohexanone monooxygenase (CHMO) from Acinetobacter calcoaceticus. Lactones possessing tetrasubstituted stereocenters are obtained with high enantioselectivity (up to >99% ee) and complete chemoselectivity. Preparative scale biotransformations were exploited in conjunction with a SmI2-mediated cyclization process to access complex, enantiomerically enriched cycloheptan- and cycloctan-1,4-diols. In a parallel approach to structurally distinct products, enantioenriched ketones from the resolution bearing an alpha- all carbon quaternary stereocenter were used in a SmI2-mediated cyclization process to give cyclobutanol products (up to >99% ee).

AB - Cyclic ketones bearing alpha-quaternary stereocenters undergo efficient kinetic resolution using cyclohexanone monooxygenase (CHMO) from Acinetobacter calcoaceticus. Lactones possessing tetrasubstituted stereocenters are obtained with high enantioselectivity (up to >99% ee) and complete chemoselectivity. Preparative scale biotransformations were exploited in conjunction with a SmI2-mediated cyclization process to access complex, enantiomerically enriched cycloheptan- and cycloctan-1,4-diols. In a parallel approach to structurally distinct products, enantioenriched ketones from the resolution bearing an alpha- all carbon quaternary stereocenter were used in a SmI2-mediated cyclization process to give cyclobutanol products (up to >99% ee).

KW - Journal Article

UR - http://www.scopus.com/inward/record.url?scp=85043320589&partnerID=8YFLogxK

U2 - 10.1002/anie.201800121

DO - 10.1002/anie.201800121

M3 - Article

C2 - 29393988

VL - 57

SP - 3692

EP - 3696

JO - Angewandte Chemie International Edition

JF - Angewandte Chemie International Edition

SN - 1433-7851

IS - 14

ER -

Biocatalytic Conversion of Cyclic Ketones Bearing α-Quaternary Stereocenters into Lactones in an Enantioselective Radical Approach to Medium-Sized Carbocycles

Abstract

Bibliographical note

Keywords

Access to Document

Other files and links

Gideon James Grogan

Cite this

Biocatalytic Conversion of Cyclic Ketones Bearing α-Quaternary Stereocenters into Lactones in an Enantioselective Radical Approach to Medium-Sized Carbocycles

Abstract

Bibliographical note

Keywords

Access to Document

Other files and links

Profiles

Gideon James Grogan

Cite this