Iridium‐Catalyzed Enantioselective [2+2+2] Cycloaddition of Diynes and Monoalkynes for the Generation of Axial Chiralities

Shibata, Takanori; Arai, Yoshikazu; Takami, Kyoko; Tsuchikama, Kyoji; Fujimoto, Takayoshi; Takebayashi, Satoshi; Takagi, Kentaro

doi:10.1002/adsc.200600317

Cited by 50 publications

(23 citation statements)

References 22 publications

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“…As expected, ees increased from 82 to 93% when lowering the temperature from 20 to -20°C (R = Ph). The origin of the enantioselectivity was attributed to cycloaddition of diynes with monoalkynes (reactions similar to those described in Scheme 7.4), they screened the influence of various parameters [216]. They observed that in most cases the temperature (rt to 100°C) and the nature of Z, Ar or R did not dramatically affect the ee value, underlying the robustness of the reaction.…”

Section: Co Catalystsmentioning

confidence: 93%

Synthesis of axially chiral biaryl compounds by asymmetric catalytic reactions with transition metals

Loxq

Manoury

Poli

et al. 2016

Coordination Chemistry Reviews

295

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Please cite this article as: P. Loxq, E. Manoury, R. Poli, E. Deydier, A. Labande, Synthesis of axially chiral biaryl compounds by asymmetric catalytic reactions with transition metals, Coordination Chemistry Reviews (2015), http://dx. AbstractAxially chiral biaryl structures are unique systems encountered in various synthetic compounds such as BINAP and BINOL, polymers, but also in natural products presenting a pharmaceutical interest such as Vancomycin, Steganacin or Korupensamine. The axial chirality of these products, so-called atropisomerism, is induced by the restricted rotation around the aryl-aryl bond. This review will summarize the different strategies imagined by chemists to control such chirality, focusing on asymmetric catalytic processes with transition metals. Only transition metal complexes bearing chiral ligands will be considered and the core of this review will consist of the enantioselective coupling of two achiral substrates. Highlights 1. A review on the synthesis of axially chiral biaryls by asymmetric catalysis 2. Exhaustive description of chiral ligands used in the palladium-catalyzed SuzukiMiyaura cross-coupling reaction 3. Emerging reactions such as asymmetric direct C-H functionalization are presented 4. Asymmetric [2+2+2] cycloadditions catalyzed by group 9 transition metals are included

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Section: Co Catalystsmentioning

confidence: 93%

Synthesis of axially chiral biaryl compounds by asymmetric catalytic reactions with transition metals

Loxq

Manoury

Poli

et al. 2016

Coordination Chemistry Reviews

295

View full text Add to dashboard Cite

show abstract

“…In 2004, they presented the first [2+2+2] cycloadditions of diynes with bis-propargylic partners, using a combination of [Ir(cod)Cl] 2 and (S,S)-Me-Duphos as catalytic system to obtain teraryl compounds with high enantio-and diastereoselectivities (Scheme 21). [51] Triynes also represent valuable candidates for this reaction, furnishing the corresponding atropoisomeric 1,2diarylbenzene derivatives with high yields and selectivities. [51] Triynes also represent valuable candidates for this reaction, furnishing the corresponding atropoisomeric 1,2diarylbenzene derivatives with high yields and selectivities.…”

Section: Iridium Catalysismentioning

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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“…Shibata et al reported iridium(I)/( S,S )‐MeDUPHOS catalyzed [2 + 2 + 2] cycloaddition of unsymmetrical diyne 30 gave an axially chiral biaryl 31 in a good yield and ee (entry 9) [8]. The bulkiness of substituents on the alkyne was very important.…”

Section: Construction Of Axial Chiralitymentioning

confidence: 99%

Recent development for enantioselective synthesis of aromatic compounds from alkynes via metallacyclopentadienes

Shi

Zhou

Kanno

et al. 2011

Journal of Heterocyclic Chem

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Iridium‐Catalyzed Enantioselective [2+2+2] Cycloaddition of Diynes and Monoalkynes for the Generation of Axial Chiralities

Cited by 50 publications

References 22 publications

Synthesis of axially chiral biaryl compounds by asymmetric catalytic reactions with transition metals

Synthesis of axially chiral biaryl compounds by asymmetric catalytic reactions with transition metals

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

Recent development for enantioselective synthesis of aromatic compounds from alkynes via metallacyclopentadienes

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