Synthesis of Cyclic Alkenyl Dimethylsiloxanes from Alkynyl Benzyldimethylsilanes and Application in Polyene Synthesis

Haraldur G. Gudmundsson; Christian J. Kuper; Damien Cornut; Felix Urbitsch; Bryony L. Elbert; Edward A. Anderson

doi:10.1021/acs.joc.9b01664

Synthesis of Cyclic Alkenyl Dimethylsiloxanes from Alkynyl Benzyldimethylsilanes and Application in Polyene Synthesis

Haraldur G. Gudmundsson, Christian J. Kuper, Damien Cornut, Felix Urbitsch, Bryony L. Elbert, Edward A. Anderson^*

^*Corresponding author for this work

Faculty of Pharmaceutical Sciences

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

5 Citations (Scopus)

Abstract

Cyclic dimethylalkenylsiloxanes, useful motifs for (Z)-selective Hiyama cross-coupling, are accessed from alkynyl benzyldimethylsilanes featuring adjacent allylic or homoallylic oxygen substituents by semihydrogenation/debenzylation/cyclization. While formation of 5- and 6-membered rings can be achieved from the free alcohols using fluoride or silanolate, allylic acetate precursors to 5-membered rings display distinct modes of activation. The utility of these compounds is demonstrated through the preparation of a variety of (Z)-alkene-containing polyenes and application to a concise total synthesis of leukotriene B₃.

Original language	English
Journal	Journal of Organic Chemistry
DOIs	https://doi.org/10.1021/acs.joc.9b01664
Publication status	Published - 2019

Bibliographical note

Funding Information:
The research leading to these results has received funding from the People Programme (Marie Curie Actions) of the European Union’s Seventh Framework Programme (FP7/2007-2013) under REA Grant 316955 (studentship to C.K.). D.C. thanks the Fondation Wiener-Anspach for a Fellowship. F.U. thanks the EPSRC Centre for Doctoral Training in Synthesis for Biology and Medicine (EP/L015838/1) for a studentship, generously supported by AstraZeneca, Diamond Light Source, Defence Science and Technology Laboratory, Evotec, GlaxoSmithKline, Janssen, Novartis, Pfizer, Syngenta, Takeda, UCB and Vertex. EAA thanks the EPSRC for additional support (EP/M019195/1).

Funding Information:
The research leading to these results has received funding from the People Programme (Marie Curie Actions) of the European Union's Seventh Framework Programme (FP7/2007-2013) under REA Grant 316955 (studentship to C.K.). D.C. thanks the Fondation Wiener-Anspach for a Fellowship. F.U. thanks the EPSRC Centre for Doctoral Training in Synthesis for Biology and Medicine (EP/L015838/1) for a studentship generously supported by AstraZeneca, Diamond Light Source, Defence Science and Technology Laboratory, Evotec, GlaxoSmithKline, Janssen Novartis, Pfizer, Syngenta, Takeda, UCB and Vertex. EAA thanks the EPSRC for additional support (EP/M019195/1).

Publisher Copyright:
© 2019 American Chemical Society.

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10.1021/acs.joc.9b01664

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title = "Synthesis of Cyclic Alkenyl Dimethylsiloxanes from Alkynyl Benzyldimethylsilanes and Application in Polyene Synthesis",

abstract = "Cyclic dimethylalkenylsiloxanes, useful motifs for (Z)-selective Hiyama cross-coupling, are accessed from alkynyl benzyldimethylsilanes featuring adjacent allylic or homoallylic oxygen substituents by semihydrogenation/debenzylation/cyclization. While formation of 5- and 6-membered rings can be achieved from the free alcohols using fluoride or silanolate, allylic acetate precursors to 5-membered rings display distinct modes of activation. The utility of these compounds is demonstrated through the preparation of a variety of (Z)-alkene-containing polyenes and application to a concise total synthesis of leukotriene B3.",

author = "Gudmundsson, {Haraldur G.} and Kuper, {Christian J.} and Damien Cornut and Felix Urbitsch and Elbert, {Bryony L.} and Anderson, {Edward A.}",

note = "Funding Information: The research leading to these results has received funding from the People Programme (Marie Curie Actions) of the European Union{\textquoteright}s Seventh Framework Programme (FP7/2007-2013) under REA Grant 316955 (studentship to C.K.). D.C. thanks the Fondation Wiener-Anspach for a Fellowship. F.U. thanks the EPSRC Centre for Doctoral Training in Synthesis for Biology and Medicine (EP/L015838/1) for a studentship, generously supported by AstraZeneca, Diamond Light Source, Defence Science and Technology Laboratory, Evotec, GlaxoSmithKline, Janssen, Novartis, Pfizer, Syngenta, Takeda, UCB and Vertex. EAA thanks the EPSRC for additional support (EP/M019195/1). Funding Information: The research leading to these results has received funding from the People Programme (Marie Curie Actions) of the European Union's Seventh Framework Programme (FP7/2007-2013) under REA Grant 316955 (studentship to C.K.). D.C. thanks the Fondation Wiener-Anspach for a Fellowship. F.U. thanks the EPSRC Centre for Doctoral Training in Synthesis for Biology and Medicine (EP/L015838/1) for a studentship generously supported by AstraZeneca, Diamond Light Source, Defence Science and Technology Laboratory, Evotec, GlaxoSmithKline, Janssen Novartis, Pfizer, Syngenta, Takeda, UCB and Vertex. EAA thanks the EPSRC for additional support (EP/M019195/1). Publisher Copyright: {\textcopyright} 2019 American Chemical Society.",

year = "2019",

doi = "10.1021/acs.joc.9b01664",

language = "English",

journal = "Journal of Organic Chemistry",

issn = "0022-3263",

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AU - Kuper, Christian J.

AU - Cornut, Damien

AU - Urbitsch, Felix

AU - Elbert, Bryony L.

AU - Anderson, Edward A.

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PY - 2019

Y1 - 2019

N2 - Cyclic dimethylalkenylsiloxanes, useful motifs for (Z)-selective Hiyama cross-coupling, are accessed from alkynyl benzyldimethylsilanes featuring adjacent allylic or homoallylic oxygen substituents by semihydrogenation/debenzylation/cyclization. While formation of 5- and 6-membered rings can be achieved from the free alcohols using fluoride or silanolate, allylic acetate precursors to 5-membered rings display distinct modes of activation. The utility of these compounds is demonstrated through the preparation of a variety of (Z)-alkene-containing polyenes and application to a concise total synthesis of leukotriene B3.

AB - Cyclic dimethylalkenylsiloxanes, useful motifs for (Z)-selective Hiyama cross-coupling, are accessed from alkynyl benzyldimethylsilanes featuring adjacent allylic or homoallylic oxygen substituents by semihydrogenation/debenzylation/cyclization. While formation of 5- and 6-membered rings can be achieved from the free alcohols using fluoride or silanolate, allylic acetate precursors to 5-membered rings display distinct modes of activation. The utility of these compounds is demonstrated through the preparation of a variety of (Z)-alkene-containing polyenes and application to a concise total synthesis of leukotriene B3.

UR - http://www.scopus.com/inward/record.url?scp=85074718897&partnerID=8YFLogxK

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DO - 10.1021/acs.joc.9b01664

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AN - SCOPUS:85074718897

SN - 0022-3263

JO - Journal of Organic Chemistry

JF - Journal of Organic Chemistry

ER -

Synthesis of Cyclic Alkenyl Dimethylsiloxanes from Alkynyl Benzyldimethylsilanes and Application in Polyene Synthesis

Abstract

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