Cyclizations of enynes catalyzed by PtCl2or other transition metal chlorides: Divergent reaction pathways

Chemistry

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https://doi.org/10.1021/ja0112184
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Cyclizations of enynes catalyzed by PtCl2or other transition metal chlorides: Divergent reaction pathways. / Méndez, María; Munoz-Herranz, Maria; Nevado, Cristina et al.
In: Journal of the American Chemical Society, Vol. 123, No. 43, 04.10.2001, p. 10511-10520.

Research output: Contribution to Journal/Magazine › Journal article › peer-review

Harvard

Méndez, M, Munoz-Herranz, M, Nevado, C, Cárdenas, DJ & Echavarren, AM 2001, 'Cyclizations of enynes catalyzed by PtCl2or other transition metal chlorides: Divergent reaction pathways', Journal of the American Chemical Society, vol. 123, no. 43, pp. 10511-10520. https://doi.org/10.1021/ja0112184

APA

Méndez, M., Munoz-Herranz, M., Nevado, C., Cárdenas, D. J., & Echavarren, A. M. (2001). Cyclizations of enynes catalyzed by PtCl2or other transition metal chlorides: Divergent reaction pathways. Journal of the American Chemical Society, 123(43), 10511-10520. https://doi.org/10.1021/ja0112184

Vancouver

Méndez M, Munoz-Herranz M, Nevado C, Cárdenas DJ, Echavarren AM. Cyclizations of enynes catalyzed by PtCl2or other transition metal chlorides: Divergent reaction pathways. Journal of the American Chemical Society. 2001 Oct 4;123(43):10511-10520. doi: 10.1021/ja0112184

Author

Méndez, María ; Munoz-Herranz, Maria ; Nevado, Cristina et al. / Cyclizations of enynes catalyzed by PtCl2or other transition metal chlorides: Divergent reaction pathways. In: Journal of the American Chemical Society. 2001 ; Vol. 123, No. 43. pp. 10511-10520.

Bibtex

@article{552222a14af3493ea5d79dc1704cf1b4,

title = "Cyclizations of enynes catalyzed by PtCl2or other transition metal chlorides: Divergent reaction pathways",

abstract = "1-En-6-ynes react with alcohols or water in the presence of PtCl2 as catalyst to give carbocycles with alkoxy or hydroxy functional groups at the side chain. The reaction proceeds by anti attack of the alkene onto the (η2-alkyne)platinum complex. The formation of the C−C and C−O bonds takes place stereoselectively by trans addition of the electrophile derived from the alkyne and the nucleophile to the double bond of the enyne. Formation of five- or six-membered carbo- or heterocycles could be obtained from 1-en-6-ynes depending on the substituents on the alkene or at the tether. Although more limited in scope, Ru(II) and Au(III) chlorides also give rise to alkoxy- or hydroxycyclization of enynes. On the basis of density functional theory (DFT) calculations, a cyclopropyl platinacarbene complex was found as the key intermediate in the process. In the presence of polar, nonnucleophilic solvents, 1-en-6-ynes are cycloisomerized with PtCl2 as catalyst. Formation of a platinacyclopentene intermediate is supported by DFT calculations. The reaction takes place by selective hydrogen abstraction of the trans-allylic substituent. Cycloisomerization of enynes containing disubstituted alkenes could be carried out using RuCl3 or Ru(AsPh3)4Cl2 in MeOH.",

author = "Mar{\'i}a M{\'e}ndez and Maria Munoz-Herranz and Cristina Nevado and C{\'a}rdenas, {Diego J.} and Echavarren, {Antonio M.}",

year = "2001",

month = oct,

day = "4",

doi = "10.1021/ja0112184",

language = "English",

volume = "123",

pages = "10511--10520",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "AMER CHEMICAL SOC",

number = "43",

}

RIS

TY - JOUR

T1 - Cyclizations of enynes catalyzed by PtCl2or other transition metal chlorides: Divergent reaction pathways

AU - Méndez, María

AU - Munoz-Herranz, Maria

AU - Nevado, Cristina

AU - Cárdenas, Diego J.

AU - Echavarren, Antonio M.

PY - 2001/10/4

Y1 - 2001/10/4

N2 - 1-En-6-ynes react with alcohols or water in the presence of PtCl2 as catalyst to give carbocycles with alkoxy or hydroxy functional groups at the side chain. The reaction proceeds by anti attack of the alkene onto the (η2-alkyne)platinum complex. The formation of the C−C and C−O bonds takes place stereoselectively by trans addition of the electrophile derived from the alkyne and the nucleophile to the double bond of the enyne. Formation of five- or six-membered carbo- or heterocycles could be obtained from 1-en-6-ynes depending on the substituents on the alkene or at the tether. Although more limited in scope, Ru(II) and Au(III) chlorides also give rise to alkoxy- or hydroxycyclization of enynes. On the basis of density functional theory (DFT) calculations, a cyclopropyl platinacarbene complex was found as the key intermediate in the process. In the presence of polar, nonnucleophilic solvents, 1-en-6-ynes are cycloisomerized with PtCl2 as catalyst. Formation of a platinacyclopentene intermediate is supported by DFT calculations. The reaction takes place by selective hydrogen abstraction of the trans-allylic substituent. Cycloisomerization of enynes containing disubstituted alkenes could be carried out using RuCl3 or Ru(AsPh3)4Cl2 in MeOH.

AB - 1-En-6-ynes react with alcohols or water in the presence of PtCl2 as catalyst to give carbocycles with alkoxy or hydroxy functional groups at the side chain. The reaction proceeds by anti attack of the alkene onto the (η2-alkyne)platinum complex. The formation of the C−C and C−O bonds takes place stereoselectively by trans addition of the electrophile derived from the alkyne and the nucleophile to the double bond of the enyne. Formation of five- or six-membered carbo- or heterocycles could be obtained from 1-en-6-ynes depending on the substituents on the alkene or at the tether. Although more limited in scope, Ru(II) and Au(III) chlorides also give rise to alkoxy- or hydroxycyclization of enynes. On the basis of density functional theory (DFT) calculations, a cyclopropyl platinacarbene complex was found as the key intermediate in the process. In the presence of polar, nonnucleophilic solvents, 1-en-6-ynes are cycloisomerized with PtCl2 as catalyst. Formation of a platinacyclopentene intermediate is supported by DFT calculations. The reaction takes place by selective hydrogen abstraction of the trans-allylic substituent. Cycloisomerization of enynes containing disubstituted alkenes could be carried out using RuCl3 or Ru(AsPh3)4Cl2 in MeOH.

U2 - 10.1021/ja0112184

DO - 10.1021/ja0112184

M3 - Journal article

VL - 123

SP - 10511

EP - 10520

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 43

ER -

Research

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