An Enantioselective Cascade Cyclopropanation Reaction Catalyzed by Rhodium(I): Asymmetric Synthesis of Vinylcyclopropanes

Torres, Òscar; Roglans, Anna; Pla‐Quintana, Anna

doi:10.1002/adsc.201600789

Cited by 22 publications

(7 citation statements)

References 67 publications

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“…On the basis of 1 H– 1 H and 1 H– 13 C correlation NMR spectra as well as GC–MS analysis we had assigned the structures of these products as the cyclopropane derivatives with internal 4 and exocyclic 5 double bonds (Scheme 2). Our spectral data correlate well with that of similar compounds, which were recently prepared by the rhodium-catalyzed cyclopropanation [44]. Compounds 4 and 5 were obtained as mixtures with approximately 1:1 ratio and total 80–90% yields.…”

Section: Resultssupporting

confidence: 84%

Unpredictable cycloisomerization of 1,11-dien-6-ynes by a common cobalt catalyst

Suleymanov¹,

Vasilyev²,

Novikov³

et al. 2017

Beilstein J. Org. Chem.

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1,11-Dien-6-ynes undergo cycloisomerization in the presence of the cobalt catalytic system CoBr2/phosphine ligand/Zn/ZnI2 giving cyclohexene, diene or cyclopropane structures depending on the type of the phosphine ligand. This unpredictable behaviour suggests that, although the availability of the cobalt catalytic system is appealing, the development of well-defined catalysts is desirable for further progress.

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Section: Resultssupporting

confidence: 84%

Unpredictable cycloisomerization of 1,11-dien-6-ynes by a common cobalt catalyst

Suleymanov¹,

Vasilyev²,

Novikov³

et al. 2017

Beilstein J. Org. Chem.

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“…1c, reaction 1). Moreover, we generalize this strategy for asymmetric cascade reaction, in which the donor/donor carbene is generated in situ via a dual carbene/alkyne metathesis (CAM) process [46][47][48][49][50][51][52][53][54] , and directly construction of polycyclic 9-aryl fluorenes with high enantioselectivity ( Fig. 1c, reaction 2) 55,56 .…”

mentioning

confidence: 99%

Transient-axial-chirality controlled asymmetric rhodium-carbene C(sp2)-H functionalization for the synthesis of chiral fluorenes

et al. 2020

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In catalytic asymmetric reactions, the formation of chiral molecules generally relies on a direct chirality transfer (point or axial chirality) from a chiral catalyst to products in the stereo-determining step. Herein, we disclose a transient-axial-chirality transfer strategy to achieve asymmetric reaction. This method relies on transferring point chirality from the catalyst to a dirhodium carbene intermediate with axial chirality, namely a transient-axialchirality since this species is an intermediate of the reaction. The transient chirality is then transferred to the final product by C(sp 2)-H functionalization reaction with exceptionally high enantioselectivity. We also generalize this strategy for the asymmetric cascade reaction involving dual carbene/alkyne metathesis (CAM), a transition-metal-catalyzed method to access chiral 9-aryl fluorene frameworks in high yields with up to 99% ee. Detailed DFT calculations shed light on the mode of the transient-axial-chirality transfer and the detailed mechanism of the CAM reaction.

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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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An Enantioselective Cascade Cyclopropanation Reaction Catalyzed by Rhodium(I): Asymmetric Synthesis of Vinylcyclopropanes

Cited by 22 publications

References 67 publications

Unpredictable cycloisomerization of 1,11-dien-6-ynes by a common cobalt catalyst

Unpredictable cycloisomerization of 1,11-dien-6-ynes by a common cobalt catalyst

Transient-axial-chirality controlled asymmetric rhodium-carbene C(sp2)-H functionalization for the synthesis of chiral fluorenes

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

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