Facial stereoselectivity in the diels-alder reactions of (arylethynyl)ethoxycarbenes of group 6 with 1,2,3,4,5-pentamethylcyclopenta-1,3- diene and unusual Rearrangement of strained norbornadienyl fischer carbene complexes of chromium(0)

Miguel A. Vázquez; Leonor Reyes; René Miranda; Juventino J. García; Hugo A. Jiménez-Vázquez; Joaquín Tamariz; Francisco Delgado

doi:10.1021/om050159q

Facial stereoselectivity in the diels-alder reactions of (arylethynyl)ethoxycarbenes of group 6 with 1,2,3,4,5-pentamethylcyclopenta-1,3- diene and unusual Rearrangement of strained norbornadienyl fischer carbene complexes of chromium(0)

Miguel A. Vázquez, Leonor Reyes, René Miranda, Juventino J. García, Hugo A. Jiménez-Vázquez, Joaquín Tamariz, Francisco Delgado

Escuela Nacional de Ciencias Biológicas (ENCB)

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27 Scopus citations

Abstract

A study of reactivity and facial selectivity in Diels-Alder reactions of the Fischer carbene complexes (CO)₅M=C(C≡CC₆H ₄R)OCH₃CH₃ (1a, M = Cr, R = H; 1b, M = Cr, R = p-OCH₃; 1c, M = Cr, R = p-CH₃; 2, M = W, R = H; 3, M = Mo, R = H), with 1,2,3,4,5-pentamethylcyclopenta-1,3-diene (4) was carried out. The cycloadditions were found to be highly π-facial stereoselective, favoring the anti adduct. Among these complexes, 3 was the most reactive dienophile. The stereochemical assignment of the adducts 5-7 was supported by NOE measurements; structures of the anti cycloadducts 5a and 6 were established by single-crystal X-ray diffraction. A [4 + 2] cycloaddition/benzannulation/rearrangement cascade reaction was observed for the chromium carbene complexes 1a-c with 4 under thermal conditions, resulting in the naphthofurandione derivatives 9-11.

Original language	English
Pages (from-to)	3413-3421
Number of pages	9
Journal	Organometallics
Volume	24
Issue number	14
DOIs	https://doi.org/10.1021/om050159q
State	Published - 4 Jul 2005

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Vázquez, M. A., Reyes, L., Miranda, R., García, J. J., Jiménez-Vázquez, H. A., Tamariz, J., & Delgado, F. (2005). Facial stereoselectivity in the diels-alder reactions of (arylethynyl)ethoxycarbenes of group 6 with 1,2,3,4,5-pentamethylcyclopenta-1,3- diene and unusual Rearrangement of strained norbornadienyl fischer carbene complexes of chromium(0). Organometallics, 24(14), 3413-3421. https://doi.org/10.1021/om050159q

@article{09461104fb83419a8b4c3ab8b1ae50ea,

title = "Facial stereoselectivity in the diels-alder reactions of (arylethynyl)ethoxycarbenes of group 6 with 1,2,3,4,5-pentamethylcyclopenta-1,3- diene and unusual Rearrangement of strained norbornadienyl fischer carbene complexes of chromium(0)",

abstract = "A study of reactivity and facial selectivity in Diels-Alder reactions of the Fischer carbene complexes (CO)5M=C(C≡CC6H 4R)OCH3CH3 (1a, M = Cr, R = H; 1b, M = Cr, R = p-OCH3; 1c, M = Cr, R = p-CH3; 2, M = W, R = H; 3, M = Mo, R = H), with 1,2,3,4,5-pentamethylcyclopenta-1,3-diene (4) was carried out. The cycloadditions were found to be highly π-facial stereoselective, favoring the anti adduct. Among these complexes, 3 was the most reactive dienophile. The stereochemical assignment of the adducts 5-7 was supported by NOE measurements; structures of the anti cycloadducts 5a and 6 were established by single-crystal X-ray diffraction. A [4 + 2] cycloaddition/benzannulation/rearrangement cascade reaction was observed for the chromium carbene complexes 1a-c with 4 under thermal conditions, resulting in the naphthofurandione derivatives 9-11.",

author = "V{\'a}zquez, {Miguel A.} and Leonor Reyes and Ren{\'e} Miranda and Garc{\'i}a, {Juventino J.} and Jim{\'e}nez-V{\'a}zquez, {Hugo A.} and Joaqu{\'i}n Tamariz and Francisco Delgado",

year = "2005",

month = jul,

day = "4",

doi = "10.1021/om050159q",

language = "Ingl{\'e}s",

volume = "24",

pages = "3413--3421",

journal = "Organometallics",

issn = "0276-7333",

number = "14",

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Vázquez, MA, Reyes, L, Miranda, R, García, JJ, Jiménez-Vázquez, HA , Tamariz, J & Delgado, F 2005, 'Facial stereoselectivity in the diels-alder reactions of (arylethynyl)ethoxycarbenes of group 6 with 1,2,3,4,5-pentamethylcyclopenta-1,3- diene and unusual Rearrangement of strained norbornadienyl fischer carbene complexes of chromium(0)', Organometallics, vol. 24, no. 14, pp. 3413-3421. https://doi.org/10.1021/om050159q

Facial stereoselectivity in the diels-alder reactions of (arylethynyl)ethoxycarbenes of group 6 with 1,2,3,4,5-pentamethylcyclopenta-1,3- diene and unusual Rearrangement of strained norbornadienyl fischer carbene complexes of chromium(0). / Vázquez, Miguel A.; Reyes, Leonor; Miranda, René et al.
In: Organometallics, Vol. 24, No. 14, 04.07.2005, p. 3413-3421.

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

TY - JOUR

T1 - Facial stereoselectivity in the diels-alder reactions of (arylethynyl)ethoxycarbenes of group 6 with 1,2,3,4,5-pentamethylcyclopenta-1,3- diene and unusual Rearrangement of strained norbornadienyl fischer carbene complexes of chromium(0)

AU - Vázquez, Miguel A.

AU - Reyes, Leonor

AU - Miranda, René

AU - García, Juventino J.

AU - Jiménez-Vázquez, Hugo A.

AU - Tamariz, Joaquín

AU - Delgado, Francisco

PY - 2005/7/4

Y1 - 2005/7/4

N2 - A study of reactivity and facial selectivity in Diels-Alder reactions of the Fischer carbene complexes (CO)5M=C(C≡CC6H 4R)OCH3CH3 (1a, M = Cr, R = H; 1b, M = Cr, R = p-OCH3; 1c, M = Cr, R = p-CH3; 2, M = W, R = H; 3, M = Mo, R = H), with 1,2,3,4,5-pentamethylcyclopenta-1,3-diene (4) was carried out. The cycloadditions were found to be highly π-facial stereoselective, favoring the anti adduct. Among these complexes, 3 was the most reactive dienophile. The stereochemical assignment of the adducts 5-7 was supported by NOE measurements; structures of the anti cycloadducts 5a and 6 were established by single-crystal X-ray diffraction. A [4 + 2] cycloaddition/benzannulation/rearrangement cascade reaction was observed for the chromium carbene complexes 1a-c with 4 under thermal conditions, resulting in the naphthofurandione derivatives 9-11.

AB - A study of reactivity and facial selectivity in Diels-Alder reactions of the Fischer carbene complexes (CO)5M=C(C≡CC6H 4R)OCH3CH3 (1a, M = Cr, R = H; 1b, M = Cr, R = p-OCH3; 1c, M = Cr, R = p-CH3; 2, M = W, R = H; 3, M = Mo, R = H), with 1,2,3,4,5-pentamethylcyclopenta-1,3-diene (4) was carried out. The cycloadditions were found to be highly π-facial stereoselective, favoring the anti adduct. Among these complexes, 3 was the most reactive dienophile. The stereochemical assignment of the adducts 5-7 was supported by NOE measurements; structures of the anti cycloadducts 5a and 6 were established by single-crystal X-ray diffraction. A [4 + 2] cycloaddition/benzannulation/rearrangement cascade reaction was observed for the chromium carbene complexes 1a-c with 4 under thermal conditions, resulting in the naphthofurandione derivatives 9-11.

UR - http://www.scopus.com/inward/record.url?scp=22444439263&partnerID=8YFLogxK

U2 - 10.1021/om050159q

DO - 10.1021/om050159q

M3 - Artículo

SN - 0276-7333

VL - 24

SP - 3413

EP - 3421

JO - Organometallics

JF - Organometallics

IS - 14

ER -

Vázquez MA, Reyes L, Miranda R, García JJ, Jiménez-Vázquez HA , Tamariz J et al. Facial stereoselectivity in the diels-alder reactions of (arylethynyl)ethoxycarbenes of group 6 with 1,2,3,4,5-pentamethylcyclopenta-1,3- diene and unusual Rearrangement of strained norbornadienyl fischer carbene complexes of chromium(0). Organometallics. 2005 Jul 4;24(14):3413-3421. doi: 10.1021/om050159q

Facial stereoselectivity in the diels-alder reactions of (arylethynyl)ethoxycarbenes of group 6 with 1,2,3,4,5-pentamethylcyclopenta-1,3- diene and unusual Rearrangement of strained norbornadienyl fischer carbene complexes of chromium(0)

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