Stereospecific Ring Contraction of Bromocycloheptenes through Dyotropic Rearrangements via Nonclassical Carbocation-Anion Pairs

Shermin S. Goh; Pier Alexandre Champagne; Sureshbabu Guduguntla; Takashi Kikuchi; Makoto Fujita; K. N. Houk; Ben L. Feringa

doi:10.1021/jacs.8b00821

Stereospecific Ring Contraction of Bromocycloheptenes through Dyotropic Rearrangements via Nonclassical Carbocation-Anion Pairs

Shermin S. Goh, Pier Alexandre Champagne, Sureshbabu Guduguntla, Takashi Kikuchi, Makoto Fujita, K. N. Houk^*, Ben L. Feringa^*

^*Corresponding author voor dit werk

Onderzoeksoutput: Article › Academic › peer review

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Experimental and theoretical evidence is reported for a rare type I dyotropic rearrangement involving a [1,2]-alkene shift, leading to the regio- and stereospecific ring contraction of bromocycloheptenes. This reaction occurs under mild conditions, with or without a Lewis acid catalyst. DFT calculations show that the reaction proceeds through a nonclassical carbocation-anion pair, which is crucial for the low activation barrier and enantiospecificity. The chiral cyclopropylcarbinyl cation may be a transition state or an intermediate, depending on the reaction conditions.

Originele taal-2	English
Pagina's (van-tot)	4986-4990
Aantal pagina's	5
Tijdschrift	Journal of the American Chemical Society
Volume	140
Nummer van het tijdschrift	15
DOI's	https://doi.org/10.1021/jacs.8b00821
Status	Published - 18-apr.-2018

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10.1021/jacs.8b00821Licentie: CC BY-NC-ND

Stereospeci fi c Ring Contraction of Bromocycloheptenes through Dyotropic Rearrangements via Nonclassical Carbocation − Anion PairsFinal publisher's version, 1,81 MBLicentie: CC BY-NC-ND

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CCDC 1571256: Experimental Crystal Structure Determination
Goh, S. S. (Contributor), Champagne, P. A. (Contributor), Guduguntla, S. (Contributor), Kikuchi, T. (Contributor), Fujita, M. (Contributor), Houk, K. N. (Contributor) & Feringa, B. L. (Contributor), University of Groningen, 29-aug.-2017
DOI: 10.5517/ccdc.csd.cc1pr0p4
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@article{e68a856304134eb68e299417c8408339,

title = "Stereospecific Ring Contraction of Bromocycloheptenes through Dyotropic Rearrangements via Nonclassical Carbocation-Anion Pairs",

abstract = "Experimental and theoretical evidence is reported for a rare type I dyotropic rearrangement involving a [1,2]-alkene shift, leading to the regio- and stereospecific ring contraction of bromocycloheptenes. This reaction occurs under mild conditions, with or without a Lewis acid catalyst. DFT calculations show that the reaction proceeds through a nonclassical carbocation-anion pair, which is crucial for the low activation barrier and enantiospecificity. The chiral cyclopropylcarbinyl cation may be a transition state or an intermediate, depending on the reaction conditions.",

keywords = "ALLYLIC SUBSTITUTION-REACTIONS, SYMMETRY CONTROLLED REACTIONS, BETA-LACTONES, ENANTIOSELECTIVE SYNTHESIS, ALLYLCARBINYL DERIVATIVES, INTERCONVERSION REACTIONS, CONJUGATE ADDITION, GRIGNARD-REAGENTS, CYCLOPROPYLCARBINYL, BUTYROLACTONES",

author = "Goh, \{Shermin S.\} and Champagne, \{Pier Alexandre\} and Sureshbabu Guduguntla and Takashi Kikuchi and Makoto Fujita and Houk, \{K. N.\} and Feringa, \{Ben L.\}",

year = "2018",

month = apr,

day = "18",

doi = "10.1021/jacs.8b00821",

language = "English",

volume = "140",

pages = "4986--4990",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "AMER CHEMICAL SOC",

number = "15",

}

TY - JOUR

T1 - Stereospecific Ring Contraction of Bromocycloheptenes through Dyotropic Rearrangements via Nonclassical Carbocation-Anion Pairs

AU - Goh, Shermin S.

AU - Champagne, Pier Alexandre

AU - Guduguntla, Sureshbabu

AU - Kikuchi, Takashi

AU - Fujita, Makoto

AU - Houk, K. N.

AU - Feringa, Ben L.

PY - 2018/4/18

Y1 - 2018/4/18

N2 - Experimental and theoretical evidence is reported for a rare type I dyotropic rearrangement involving a [1,2]-alkene shift, leading to the regio- and stereospecific ring contraction of bromocycloheptenes. This reaction occurs under mild conditions, with or without a Lewis acid catalyst. DFT calculations show that the reaction proceeds through a nonclassical carbocation-anion pair, which is crucial for the low activation barrier and enantiospecificity. The chiral cyclopropylcarbinyl cation may be a transition state or an intermediate, depending on the reaction conditions.

AB - Experimental and theoretical evidence is reported for a rare type I dyotropic rearrangement involving a [1,2]-alkene shift, leading to the regio- and stereospecific ring contraction of bromocycloheptenes. This reaction occurs under mild conditions, with or without a Lewis acid catalyst. DFT calculations show that the reaction proceeds through a nonclassical carbocation-anion pair, which is crucial for the low activation barrier and enantiospecificity. The chiral cyclopropylcarbinyl cation may be a transition state or an intermediate, depending on the reaction conditions.

KW - ALLYLIC SUBSTITUTION-REACTIONS

KW - SYMMETRY CONTROLLED REACTIONS

KW - BETA-LACTONES

KW - ENANTIOSELECTIVE SYNTHESIS

KW - ALLYLCARBINYL DERIVATIVES

KW - INTERCONVERSION REACTIONS

KW - CONJUGATE ADDITION

KW - GRIGNARD-REAGENTS

KW - CYCLOPROPYLCARBINYL

KW - BUTYROLACTONES

U2 - 10.1021/jacs.8b00821

DO - 10.1021/jacs.8b00821

M3 - Article

SN - 0002-7863

VL - 140

SP - 4986

EP - 4990

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 15

ER -

Stereospecific Ring Contraction of Bromocycloheptenes through Dyotropic Rearrangements via Nonclassical Carbocation-Anion Pairs

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CCDC 1571256: Experimental Crystal Structure Determination

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