Versatile and regioselective synthesis of polysubstituted and highly oxygenated phenols via Dötz reaction of α-alkoxyvinyl(ethoxy)carbene complexes with alkynes

Mabel M. Montenegro, José Luis Vega-Báez, Miguel A. Vázquez, Ma Inés Flores-Conde, Arturo Sánchez, Miguel A. González-Tototzin, Rsuini U. Gutiérrez, J. Miguel Lazcano-Seres, Francisco Ayala, L. Gerardo Zepeda, Joaquín Tamariz, Francisco Delgado

Research output: Contribution to journalArticle

4 Citations (Scopus)

Abstract

© 2016 Elsevier B.V. A comparative study of reactivity and selectivity of α-alkoxyvinyl(ethoxy) Fischer carbene complexes (CO)5M = C[C(=CHR1)(OR)]OCH2CH3 [7a–d: M = Cr; 12a–c: M = Mo; 13a–d: M = W; a: R1 = H, R = CH2CH3; b: R1 = H, R = CH2CH2CH3; c: R1 = H, R = CH2CH2CH2CH3; d: R1 = CH3, R = Et (E and Z)] with terminal and internal alkynes (14a–g) in benzannulation reactions is described. The complexes 7 and 12–13 display a remarkable reactivity toward different alkynes. The [3 + 2+1] cycloaddition or benzannulation reactions between the latter carbene complexes and alkynes 14 were found to be highly regio- and chemoselective only giving those products with the largest substituent of the acetylenic component located at the ortho position to the hydroxyl group, and favoring the formation of new and highly oxygenated and polysubstituted phenols containing only electron-donating groups. The regiochemistry assignment of the cycloadducts was supported by NOE measurements. Phenols 15c, 16e, and 18b were further characterized by single-crystal X-ray diffraction.
Original languageAmerican English
Pages (from-to)41-54
Number of pages35
JournalJournal of Organometallic Chemistry
DOIs
StatePublished - 15 Dec 2016

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Alkynes
Phenols
carbenes
alkynes
phenols
Cycloaddition
synthesis
reactivity
Cycloaddition Reaction
cycloaddition
Single crystals
X-Ray Diffraction
X ray diffraction
Hydroxyl Radical
Electrons
selectivity
single crystals
products
diffraction
carbene

Cite this

Montenegro, Mabel M. ; Vega-Báez, José Luis ; Vázquez, Miguel A. ; Flores-Conde, Ma Inés ; Sánchez, Arturo ; González-Tototzin, Miguel A. ; Gutiérrez, Rsuini U. ; Lazcano-Seres, J. Miguel ; Ayala, Francisco ; Zepeda, L. Gerardo ; Tamariz, Joaquín ; Delgado, Francisco. / Versatile and regioselective synthesis of polysubstituted and highly oxygenated phenols via Dötz reaction of α-alkoxyvinyl(ethoxy)carbene complexes with alkynes. In: Journal of Organometallic Chemistry. 2016 ; pp. 41-54.
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abstract = "{\circledC} 2016 Elsevier B.V. A comparative study of reactivity and selectivity of α-alkoxyvinyl(ethoxy) Fischer carbene complexes (CO)5M = C[C(=CHR1)(OR)]OCH2CH3 [7a–d: M = Cr; 12a–c: M = Mo; 13a–d: M = W; a: R1 = H, R = CH2CH3; b: R1 = H, R = CH2CH2CH3; c: R1 = H, R = CH2CH2CH2CH3; d: R1 = CH3, R = Et (E and Z)] with terminal and internal alkynes (14a–g) in benzannulation reactions is described. The complexes 7 and 12–13 display a remarkable reactivity toward different alkynes. The [3 + 2+1] cycloaddition or benzannulation reactions between the latter carbene complexes and alkynes 14 were found to be highly regio- and chemoselective only giving those products with the largest substituent of the acetylenic component located at the ortho position to the hydroxyl group, and favoring the formation of new and highly oxygenated and polysubstituted phenols containing only electron-donating groups. The regiochemistry assignment of the cycloadducts was supported by NOE measurements. Phenols 15c, 16e, and 18b were further characterized by single-crystal X-ray diffraction.",
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Versatile and regioselective synthesis of polysubstituted and highly oxygenated phenols via Dötz reaction of α-alkoxyvinyl(ethoxy)carbene complexes with alkynes. / Montenegro, Mabel M.; Vega-Báez, José Luis; Vázquez, Miguel A.; Flores-Conde, Ma Inés; Sánchez, Arturo; González-Tototzin, Miguel A.; Gutiérrez, Rsuini U.; Lazcano-Seres, J. Miguel; Ayala, Francisco; Zepeda, L. Gerardo; Tamariz, Joaquín; Delgado, Francisco.

In: Journal of Organometallic Chemistry, 15.12.2016, p. 41-54.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Versatile and regioselective synthesis of polysubstituted and highly oxygenated phenols via Dötz reaction of α-alkoxyvinyl(ethoxy)carbene complexes with alkynes

AU - Montenegro, Mabel M.

AU - Vega-Báez, José Luis

AU - Vázquez, Miguel A.

AU - Flores-Conde, Ma Inés

AU - Sánchez, Arturo

AU - González-Tototzin, Miguel A.

AU - Gutiérrez, Rsuini U.

AU - Lazcano-Seres, J. Miguel

AU - Ayala, Francisco

AU - Zepeda, L. Gerardo

AU - Tamariz, Joaquín

AU - Delgado, Francisco

PY - 2016/12/15

Y1 - 2016/12/15

N2 - © 2016 Elsevier B.V. A comparative study of reactivity and selectivity of α-alkoxyvinyl(ethoxy) Fischer carbene complexes (CO)5M = C[C(=CHR1)(OR)]OCH2CH3 [7a–d: M = Cr; 12a–c: M = Mo; 13a–d: M = W; a: R1 = H, R = CH2CH3; b: R1 = H, R = CH2CH2CH3; c: R1 = H, R = CH2CH2CH2CH3; d: R1 = CH3, R = Et (E and Z)] with terminal and internal alkynes (14a–g) in benzannulation reactions is described. The complexes 7 and 12–13 display a remarkable reactivity toward different alkynes. The [3 + 2+1] cycloaddition or benzannulation reactions between the latter carbene complexes and alkynes 14 were found to be highly regio- and chemoselective only giving those products with the largest substituent of the acetylenic component located at the ortho position to the hydroxyl group, and favoring the formation of new and highly oxygenated and polysubstituted phenols containing only electron-donating groups. The regiochemistry assignment of the cycloadducts was supported by NOE measurements. Phenols 15c, 16e, and 18b were further characterized by single-crystal X-ray diffraction.

AB - © 2016 Elsevier B.V. A comparative study of reactivity and selectivity of α-alkoxyvinyl(ethoxy) Fischer carbene complexes (CO)5M = C[C(=CHR1)(OR)]OCH2CH3 [7a–d: M = Cr; 12a–c: M = Mo; 13a–d: M = W; a: R1 = H, R = CH2CH3; b: R1 = H, R = CH2CH2CH3; c: R1 = H, R = CH2CH2CH2CH3; d: R1 = CH3, R = Et (E and Z)] with terminal and internal alkynes (14a–g) in benzannulation reactions is described. The complexes 7 and 12–13 display a remarkable reactivity toward different alkynes. The [3 + 2+1] cycloaddition or benzannulation reactions between the latter carbene complexes and alkynes 14 were found to be highly regio- and chemoselective only giving those products with the largest substituent of the acetylenic component located at the ortho position to the hydroxyl group, and favoring the formation of new and highly oxygenated and polysubstituted phenols containing only electron-donating groups. The regiochemistry assignment of the cycloadducts was supported by NOE measurements. Phenols 15c, 16e, and 18b were further characterized by single-crystal X-ray diffraction.

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