Selective synthesis of cyclooctanoids by radical cyclization of seven-membered lactones: neutron diffraction study of the stereoselective deuteration of a chiral organosamarium

Xavier Just-Baringo; Jemma Clark; Matthias  Gutmann; David Procter

doi:10.1002/anie.201606792

Selective synthesis of cyclooctanoids by radical cyclization of seven-membered lactones: neutron diffraction study of the stereoselective deuteration of a chiral organosamarium

Xavier Just-Baringo, Jemma Clark, Matthias Gutmann, David Procter

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

Abstract

Seven-membered lactones undergo selective SmI2–H2O-promoted radical cyclization to form substituted cyclooctanols. The products arise from an exo-mode of cyclization rather than the usual endo-attack employed in the few radical syntheses of cyclooctanes. The process is terminated by the quenching of a chiral benzylic samarium. A labeling experiment and neutron diffraction study have been used for the first time to probe the configuration and highly diastereoselective deuteration of a chiral organosamarium intermediate.

Original language	English
Journal	Angewandte Chemie - International Edition
Volume	55
Issue number	40
Early online date	7 Sep 2016
DOIs	https://doi.org/10.1002/anie.201606792
Publication status	Published - 19 Sep 2016

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10.1002/anie.201606792Licence: CC BY

CCDC 1480731: Experimental Crystal Structure Determination
Just-Baringo, X. (Contributor), Clark, J. (Contributor), Gutmann, M. (Contributor) & Procter, D. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 2016
DOI: 10.5517/ccdc.csd.cc1lptjm, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc1lptjm&sid=DataCite
Dataset
CCDC 1480728: Experimental Crystal Structure Determination
Just-Baringo, X. (Contributor), Clark, J. (Contributor), Gutmann, M. (Contributor) & Procter, D. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 2017
DOI: 10.5517/ccdc.csd.cc1lptfj, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc1lptfj&sid=DataCite
Dataset
CCDC 1480730: Experimental Crystal Structure Determination
Just-Baringo, X. (Contributor), Clark, J. (Contributor), Gutmann, M. (Contributor) & Procter, D. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 2017
DOI: 10.5517/ccdc.csd.cc1lpthl, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc1lpthl&sid=DataCite
Dataset

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title = "Selective synthesis of cyclooctanoids by radical cyclization of seven-membered lactones: neutron diffraction study of the stereoselective deuteration of a chiral organosamarium",

abstract = "Seven-membered lactones undergo selective SmI2–H2O-promoted radical cyclization to form substituted cyclooctanols. The products arise from an exo-mode of cyclization rather than the usual endo-attack employed in the few radical syntheses of cyclooctanes. The process is terminated by the quenching of a chiral benzylic samarium. A labeling experiment and neutron diffraction study have been used for the first time to probe the configuration and highly diastereoselective deuteration of a chiral organosamarium intermediate.",

author = "Xavier Just-Baringo and Jemma Clark and Matthias Gutmann and David Procter",

year = "2016",

month = sep,

day = "19",

doi = "10.1002/anie.201606792",

language = "English",

volume = "55",

journal = "Angewandte Chemie. International Edition",

issn = "1433-7851",

publisher = "John Wiley & Sons Ltd",

number = "40",

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Selective synthesis of cyclooctanoids by radical cyclization of seven-membered lactones: neutron diffraction study of the stereoselective deuteration of a chiral organosamarium. / Just-Baringo, Xavier; Clark, Jemma; Gutmann, Matthias et al.

In: Angewandte Chemie - International Edition, Vol. 55, No. 40, 19.09.2016.

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

TY - JOUR

T1 - Selective synthesis of cyclooctanoids by radical cyclization of seven-membered lactones: neutron diffraction study of the stereoselective deuteration of a chiral organosamarium

AU - Just-Baringo, Xavier

AU - Clark, Jemma

AU - Gutmann, Matthias

AU - Procter, David

PY - 2016/9/19

Y1 - 2016/9/19

N2 - Seven-membered lactones undergo selective SmI2–H2O-promoted radical cyclization to form substituted cyclooctanols. The products arise from an exo-mode of cyclization rather than the usual endo-attack employed in the few radical syntheses of cyclooctanes. The process is terminated by the quenching of a chiral benzylic samarium. A labeling experiment and neutron diffraction study have been used for the first time to probe the configuration and highly diastereoselective deuteration of a chiral organosamarium intermediate.

AB - Seven-membered lactones undergo selective SmI2–H2O-promoted radical cyclization to form substituted cyclooctanols. The products arise from an exo-mode of cyclization rather than the usual endo-attack employed in the few radical syntheses of cyclooctanes. The process is terminated by the quenching of a chiral benzylic samarium. A labeling experiment and neutron diffraction study have been used for the first time to probe the configuration and highly diastereoselective deuteration of a chiral organosamarium intermediate.

U2 - 10.1002/anie.201606792

DO - 10.1002/anie.201606792

M3 - Article

VL - 55

JO - Angewandte Chemie. International Edition

JF - Angewandte Chemie. International Edition

SN - 1433-7851

IS - 40

ER -

Selective synthesis of cyclooctanoids by radical cyclization of seven-membered lactones: neutron diffraction study of the stereoselective deuteration of a chiral organosamarium

Abstract

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Datasets

CCDC 1480731: Experimental Crystal Structure Determination

CCDC 1480728: Experimental Crystal Structure Determination

CCDC 1480730: Experimental Crystal Structure Determination

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