Enantiospecific Brook Rearrangement of Tertiary Benzylic α-Hydroxysilanes

Juan F. Collados; Pablo Ortiz; Juana M. Pérez; Yiyin Xia; Mark A.J. Koenis; Wybren J. Buma; Valentin P. Nicu; Syuzanna R. Harutyunyan

doi:10.1002/ejoc.201701469

Enantiospecific Brook Rearrangement of Tertiary Benzylic α-Hydroxysilanes

Juan F. Collados, Pablo Ortiz, Juana M. Pérez, Yiyin Xia, Mark A.J. Koenis, Wybren J. Buma, Valentin P. Nicu, Syuzanna R. Harutyunyan^*

^*Corresponding author for this work

Bioeconomy and CO2

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

11 Citations (Scopus)

Abstract

The Brook rearrangement of simple, chiral tertiary benzylic α-hydroxysilanes is presented. The rearrangement followed by proton trapping is enantiospecific and proceeds with inversion of the configuration at the carbon center. Importantly, the [1,2]-Brook rearrangement can be followed by trapping of methyl or allyl electrophiles even in the protic environment, although with minimal retention of chirality.

Original language	English
Pages (from-to)	3900-3903
Number of pages	4
Journal	European Journal of Organic Chemistry
Volume	2018
Issue number	29
DOIs	https://doi.org/10.1002/ejoc.201701469
Publication status	Published - 7 Aug 2018

Funding

Financial support from The Netherlands Organization for Scientific Research (NWO-Vidi and ECHO to S. R. H.) and the Ministry of Education, Culture and Science (Gravity program 024.001.035 to S. R. H.) is acknowledged. J. M. P. thanks to the European Commission for an Intra-European Marie Curie fellowship (grant 746011 - ChirPyr). This research received further support from NWO in the framework of the Fund New Chemical Innovations (NWO Project Nr. 731.014.209).

Funders	Funder number
Fund New Chemical Innovations	731.014.209
European Commission	746011 - ChirPyr
Ministerie van Onderwijs, Cultuur en Wetenschap	024.001.035
Nederlandse Organisatie voor Wetenschappelijk Onderzoek

Keywords

Chirality
Enantiospecific
Hydroxysilanes
Rearrangement
Synthetic methods

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10.1002/ejoc.201701469

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title = "Enantiospecific Brook Rearrangement of Tertiary Benzylic α-Hydroxysilanes",

abstract = "The Brook rearrangement of simple, chiral tertiary benzylic α-hydroxysilanes is presented. The rearrangement followed by proton trapping is enantiospecific and proceeds with inversion of the configuration at the carbon center. Importantly, the [1,2]-Brook rearrangement can be followed by trapping of methyl or allyl electrophiles even in the protic environment, although with minimal retention of chirality.",

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AU - Collados, Juan F.

AU - Ortiz, Pablo

AU - Pérez, Juana M.

AU - Xia, Yiyin

AU - Koenis, Mark A.J.

AU - Buma, Wybren J.

AU - Nicu, Valentin P.

AU - Harutyunyan, Syuzanna R.

PY - 2018/8/7

Y1 - 2018/8/7

N2 - The Brook rearrangement of simple, chiral tertiary benzylic α-hydroxysilanes is presented. The rearrangement followed by proton trapping is enantiospecific and proceeds with inversion of the configuration at the carbon center. Importantly, the [1,2]-Brook rearrangement can be followed by trapping of methyl or allyl electrophiles even in the protic environment, although with minimal retention of chirality.

AB - The Brook rearrangement of simple, chiral tertiary benzylic α-hydroxysilanes is presented. The rearrangement followed by proton trapping is enantiospecific and proceeds with inversion of the configuration at the carbon center. Importantly, the [1,2]-Brook rearrangement can be followed by trapping of methyl or allyl electrophiles even in the protic environment, although with minimal retention of chirality.

KW - Chirality

KW - Enantiospecific

KW - Hydroxysilanes

KW - Rearrangement

KW - Synthetic methods

UR - http://www.scopus.com/inward/record.url?scp=85051137614&partnerID=8YFLogxK

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DO - 10.1002/ejoc.201701469

M3 - Article

AN - SCOPUS:85051137614

SN - 1434-193X

VL - 2018

SP - 3900

EP - 3903

JO - European Journal of Organic Chemistry

JF - European Journal of Organic Chemistry

IS - 29

ER -

Enantiospecific Brook Rearrangement of Tertiary Benzylic α-Hydroxysilanes

Abstract

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Keywords

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