Enantioselective Synthesis of Planar‐Chiral Carba‐Paracyclophanes: Rhodium‐Catalyzed [2+2+2] Cycloaddition of Cyclic Diynes with Terminal Monoynes

Araki, Tatsuya; Noguchi, Keiichi; Tanaka, Ken

doi:10.1002/anie.201300696

Cited by 61 publications

(22 citation statements)

References 91 publications

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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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“…Similarly, they also reported the synthesis of the planar-chiral carba-paracyclophane 278 by using the cationic rhodium(I)/( S , S )-bdpp-catalyzed [2 + 2 + 2] cycloaddition of cyclic diyne 277 with terminal methyl propiolate ( 275 ) under high substrate concentration conditions ( Scheme 46 ) [ 179 ].…”

Section: Reviewmentioning

confidence: 99%

Selected synthetic strategies to cyclophanes

Kotha¹,

Shirbhate²,

Waghule³

2015

Beilstein J. Org. Chem.

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SummaryIn this review we cover various approaches to meta- and paracyclophanes involving popular reactions. Generally, we have included a strategy where the reaction was used for assembling the cyclophane skeleton for further functionalization. In several instances, after the cyclophane is made several popular reactions are used and these are not covered here. We included various natural products related to cyclophanes. To keep the length of the review at a manageable level the literature related to orthocyclophanes was not included.

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“…[81] However, under these conditions the yields and ee values remain low. [82] An alternative strategy for the synthesis of relevant macrocyclic cyclophanes and tripodal cage compounds is the rhodium-catalyzed [2+2+2] cycloaddition of branched triynes. [82] An alternative strategy for the synthesis of relevant macrocyclic cyclophanes and tripodal cage compounds is the rhodium-catalyzed [2+2+2] cycloaddition of branched triynes.…”

Section: Construction Of Planar Chiralitymentioning

confidence: 99%

Recent Advances in Stereoselective [2+2+2] Cycloadditions

2014

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The [2+2+2] cycloaddition reaction is considered one of the most efficient methods for the rapid and straightforward preparation of complex polycyclic (and heterocyclic) compounds in a highly selective and atom‐economical fashion. Over the last half‐century, remarkable advances in terms of chemo‐ and regioselectivities have been realized, endowing this reaction with attractive features as a key step in the synthesis of various biologically active molecules and materials. The development of stereoselective methodologies is more recent. In this field, asymmetric transition‐metal catalysis has emerged as the most convenient tool with which to perform these [2+2+2] cycloadditions in their enantio‐ and diastereoselective variants. All the catalytic systems that have been developed so far are based on very close association of a transition metal (Co, Ni, Ir, Rh, ...) with a chiral ligand. The success of these reactions is then related to the reaction pattern involved (inter‐ and intramolecular), implying an efficient substrate/active species interaction. Thus, judicious design both of chiral ligands and of unsaturated substrates is necessary. In light of these aspects, numerous stereoselective cycloadditions have been reported; these allow the construction in one‐step fashion of central, axial, planar, and helical chiralities. This review details the recent advances in this area, with specific attention to catalysts and reaction scope.

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Enantioselective Synthesis of Planar‐Chiral Carba‐Paracyclophanes: Rhodium‐Catalyzed [2+2+2] Cycloaddition of Cyclic Diynes with Terminal Monoynes

Cited by 61 publications

References 91 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.

Selected synthetic strategies to cyclophanes

Recent Advances in Stereoselective [2+2+2] Cycloadditions

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