Rhodium-Catalyzed Asymmetric [2 + 2 + 2] Cycloaddition of 1,6-Enynes with Cyclopropylideneacetamides

Nakamura, Yu; Masutomi, Koji; Yoshida, Tomoka; Noguchi, Keiichi; Shibata, Yu; Tanaka, Ken

doi:10.1021/acs.orglett.5b03387

Cited by 22 publications

(5 citation statements)

References 60 publications

(17 reference statements)

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“…They are usually generated in situ in a nonpolar solvent, either DCM or dichloroethane, by hydrogenation of a cationic bis-diolefin rhodium complex, for example, [Rh(COD) 2 ]OTf, in the presence of a diphosphine like BINAP. ([2+2+2]cycloadditions: [176][177][178][179][180][181][182][183][184], hydrogen-mediated reductive C-C coupling: [185][186][187], enantioselective reductive cyclization: [188,189], intermolecular cyclotrimerization: [190][191][192][193]) It should be noted that the formation of these species and their role in catalysis is often overlooked.…”

Section: +mentioning

confidence: 99%

Activation, Deactivation and Reversibility Phenomena in Homogeneous Catalysis: A Showcase Based on the Chemistry of Rhodium/Phosphine Catalysts

et al. 2019

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In the present work, the rich chemistry of rhodium/phosphine complexes, which are applied as homogeneous catalysts to promote a wide range of chemical transformations, has been used to showcase how the in situ generation of precatalysts, the conversion of precatalysts into the actually active species, as well as the reaction of the catalyst itself with other components in the reaction medium (substrates, solvents, additives) can lead to a number of deactivation phenomena and thus impact the efficiency of a catalytic process. Such phenomena may go unnoticed or may be overlooked, thus preventing the full understanding of the catalytic process which is a prerequisite for its optimization. Based on recent findings both from others and the authors’ laboratory concerning the chemistry of rhodium/diphosphine complexes, some guidelines are provided for the optimal generation of the catalytic active species from a suitable rhodium precursor and the diphosphine of interest; for the choice of the best solvent to prevent aggregation of coordinatively unsaturated metal fragments and sequestration of the active metal through too strong metal–solvent interactions; for preventing catalyst poisoning due to irreversible reaction with the product of the catalytic process or impurities present in the substrate.

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Section: +mentioning

confidence: 99%

Activation, Deactivation and Reversibility Phenomena in Homogeneous Catalysis: A Showcase Based on the Chemistry of Rhodium/Phosphine Catalysts

et al. 2019

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“…On the other hand, our research group recently reported the Rh I+ -catalyzed [3+2+2] [7][8][9] and [2+2+2] [10,11] cycloadditions of cyclopropylideneacetamides with 1,6-diynes and two monoynes, respectivly. [12] In this paper, we disclose the unprecedented Rh I+catalyzed [2+2+1] cycloaddition of cyclopropylideneacetamides with 1,6-diynes, leading to the multi-substituted fulvenes, through releasing ethylene [13,14] (Scheme 1b bottom).…”

Section: Cyclopentadienylmentioning

confidence: 99%

“…A 1970, 2875. [5] For selected examples of synthesis of multi-substituted fulvenes via annulations, see: a [1] 1b, [2] 1c, 1d, [3] 1e, [4] 1f, [3] 1g, [5] 1j, [7] and 1k, [3] and cyclopropyllideneacetamides 2a, [8] and 2b [9] were prepared according to the literatures. All other reagents were obtained from commercial sources and used as received.…”

Section: Cyclopentadienylmentioning

confidence: 99%

Fulvene Synthesis by Rhodium(I)‐Catalyzed [2+2+1] Cycloaddition: Synthesis and Catalytic Activity of Tunable Cyclopentadienyl Rhodium(III) Complexes with Pendant Amides

2017

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It has been established that a Rh /segphos complex catalyzes the [2+2+1] cycloaddition of 1,6-diynes with cyclopropylideneacetamides to give substituted fulvenes in good yields. The reductive complexation of the product fulvenes with RhCl in EtOH furnished the corresponding dinuclear cyclopentadienyl Rh complexes bearing a pendant amide moiety. These Rh complexes were highly active catalysts for oxidative annulation and cyclization through C(sp )-H and C(sp )-H functionalization.

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“…[17] Further examples demonstrated the broadness of applicability of chiral, in situ-generated rhodium-catalyst systems. [18] Depending on the metal, different protocols were appliedt o generatet he active chiral catalyst. The efficiency of such protocols though can vary significantly,t husaffecting the amount of metal effectively available for the catalytic reaction.…”

Section: Introductionmentioning

confidence: 99%

Insight into the Activation of In Situ Generated Chiral Rh^I Catalysts and Their Application in Cyclotrimerizations

Thiel

Horstmann

Jungk

et al. 2017

Chemistry A European J

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We report a detailed study concerning the efficient generation of highly active chiral rhodium complexes of the general structure [Rh(diphosphine)(solvent) ] as well as their exemplary successful utilization as catalysts for cyclotrimerizations. Such solvent complexes could likewise be prepared from novel ammonia complexes of the type [Rh(diphosphine)(NH ) ] . A valuable, feasible approach to generate novel chiral Rh complexes was found by in situ generation from Wilkinson's catalyst [RhCl(PPh ) ] with chiral P,N ligands. The generated catalysts led to moderate to good enantioselectivities and excellent yields in the cyclotrimerizations of triynes, showcasing their usefulness in the synthesis of axially chiral benzene derivatives.

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Rhodium-Catalyzed Asymmetric [2 + 2 + 2] Cycloaddition of 1,6-Enynes with Cyclopropylideneacetamides

Abstract: It has been established that a cationic rhodium(I)/H8-BINAP complex catalyzes the asymmetric [2 + 2 + 2] cycloaddition of 1,6-enynes with cyclopropylideneacetamides to produce spirocyclohexenes in excellent enantioselectivity with retaining cyclopropane rings.

Cited by 22 publications

References 60 publications

Activation, Deactivation and Reversibility Phenomena in Homogeneous Catalysis: A Showcase Based on the Chemistry of Rhodium/Phosphine Catalysts

Activation, Deactivation and Reversibility Phenomena in Homogeneous Catalysis: A Showcase Based on the Chemistry of Rhodium/Phosphine Catalysts

Fulvene Synthesis by Rhodium(I)‐Catalyzed [2+2+1] Cycloaddition: Synthesis and Catalytic Activity of Tunable Cyclopentadienyl Rhodium(III) Complexes with Pendant Amides

Insight into the Activation of In Situ Generated Chiral Rh^I Catalysts and Their Application in Cyclotrimerizations

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Rhodium-Catalyzed Asymmetric [2 + 2 + 2] Cycloaddition of 1,6-Enynes with Cyclopropylideneacetamides

Abstract: It has been established that a cationic rhodium(I)/H8-BINAP complex catalyzes the asymmetric [2 + 2 + 2] cycloaddition of 1,6-enynes with cyclopropylideneacetamides to produce spirocyclohexenes in excellent enantioselectivity with retaining cyclopropane rings.

Cited by 22 publications

References 60 publications

Activation, Deactivation and Reversibility Phenomena in Homogeneous Catalysis: A Showcase Based on the Chemistry of Rhodium/Phosphine Catalysts

Activation, Deactivation and Reversibility Phenomena in Homogeneous Catalysis: A Showcase Based on the Chemistry of Rhodium/Phosphine Catalysts

Fulvene Synthesis by Rhodium(I)‐Catalyzed [2+2+1] Cycloaddition: Synthesis and Catalytic Activity of Tunable Cyclopentadienyl Rhodium(III) Complexes with Pendant Amides

Insight into the Activation of In Situ Generated Chiral RhI Catalysts and Their Application in Cyclotrimerizations

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Insight into the Activation of In Situ Generated Chiral Rh^I Catalysts and Their Application in Cyclotrimerizations