New synthesis of pyrrolidine derivatives via the chromacyclobutanes generated from enynes and Fischer carbene complexes

Mori, Miwako; Watanuki, Susumu

doi:10.1039/c39920001082

Cited by 30 publications

(11 citation statements)

References 9 publications

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“…On the other hand, the metathesis product 75 has usually been the main compound (29-62%) in the reaction of an aryl-enyne bearing a N-Ts substituted-tether in acetonitrile [39]. A significant role in the outcome of these reactions was played by the substituent placed in the aryl group; in fact, cyclopropanation was the main process if that substituent is a nitro group.…”

Section: Reactions With Ax-enynesmentioning

confidence: 99%

Group 6 Fischer carbene complexes: “chemical multitalents” for multi-component reactions

Barluenga

Fernández‐Rodríguez

Aguilar

2005

Journal of Organometallic Chemistry

123

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Section: Reactions With Ax-enynesmentioning

confidence: 99%

Group 6 Fischer carbene complexes: “chemical multitalents” for multi-component reactions

Barluenga

Fernández‐Rodríguez

Aguilar

2005

Journal of Organometallic Chemistry

123

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“…63 In this context, it is also necessary to re-evaluate the small number of related examples documented in the literature in which stoichiometric reactions of preformed Fischer carbene complexes with enynes resulted in either cyclopropanation or metathesis depending on the substitution pattern (and/or the solvent). 64 − 66 Fully convincing explanations have not been published, but it has been speculated that the stability of the secondary carbene generated in the case of metathesis might play a role in determining the reaction outcome. Although this looks—a priori—like a thermodynamic argument, it cannot be discounted in the first place but deserves further consideration.…”

Section: Resultsmentioning

confidence: 99%

Hydrogenative Metathesis of Enynes via Piano-Stool Ruthenium Carbene Complexes Formed by Alkyne gem-Hydrogenation

et al. 2020

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The only recently discovered gem -hydrogenation of internal alkynes is a fundamentally new transformation, in which both H atoms of dihydrogen are transferred to the same C atom of a triple bond while the other position transforms into a discrete metal carbene complex. [Cp*RuCl] 4 is presently the catalyst of choice: the resulting piano-stool ruthenium carbenes can engage a tethered alkene into either cyclopropanation or metathesis, and a prototypical example of such a reactive intermediate with an olefin ligated to the ruthenium center has been isolated and characterized by X-ray diffraction. It is the substitution pattern of the olefin that determines whether metathesis or cyclopropanation takes place: a systematic survey using alkenes of largely different character in combination with a computational study of the mechanism at the local coupled cluster level of theory allowed the preparative results to be sorted and an intuitive model with predictive power to be proposed. This model links the course of the reaction to the polarization of the double bond as well as to the stability of the secondary carbene complex formed, if metathesis were to take place. The first application of “hydrogenative metathesis” to the total synthesis of sinularones E and F concurred with this interpretation and allowed the proposed structure of these marine natural products to be confirmed. During this synthesis, it was found that gem -hydrogenation also provides opportunities for C–H functionalization. Moreover, silylated alkynes are shown to participate well in hydrogenative metathesis, which opens a new entry into valuable allylsilane building blocks. Crystallographic evidence suggests that the polarized [Ru–Cl] bond of the catalyst interacts with the neighboring R 3 Si group. Since attractive interligand Cl/R 3 Si contacts had already previously been invoked to explain the outcome of various ruthenium-catalyzed reactions, including trans -hydrosilylation, the experimental confirmation provided herein has implications beyond the present case.

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“…The catalytic enyne metathesis reaction was first discovered by Katz and Sivavec (421) (424,425), Fischer carbene complexes of chromium were shown to catalyze the enyne metathesis of 1,6-enynes in which the alkene terminus supports an alkoxy group (419,420). However, Grubbs' catalyst (426) was later found to be more broadly applicable (427,428).…”

Section: B Intramolecular Ring-closing Enyne Metathesismentioning

confidence: 99%

Unique Metal‐Diyne, ‐Enyne, and ‐Enediyne Complexes: Part of the Remarkably Diverse World of Metal‐Alkyne Chemistry

Bhattacharyya

Sangita

Zaleski

2007

Progress in Inorganic Chemistry

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New synthesis of pyrrolidine derivatives via the chromacyclobutanes generated from enynes and Fischer carbene complexes

Abstract: Pyrrolidine derivatives have been synthesized via chromacyclobutanes formed f r o m the Fischer carbene complex 2b and the aza-enyne 5a; a mechanism is suggested o n the basis of the products that are formed.

Cited by 30 publications

References 9 publications

Group 6 Fischer carbene complexes: “chemical multitalents” for multi-component reactions

Group 6 Fischer carbene complexes: “chemical multitalents” for multi-component reactions

Hydrogenative Metathesis of Enynes via Piano-Stool Ruthenium Carbene Complexes Formed by Alkyne gem-Hydrogenation

Unique Metal‐Diyne, ‐Enyne, and ‐Enediyne Complexes: Part of the Remarkably Diverse World of Metal‐Alkyne Chemistry

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