Atroposelective [2+2+2] cycloadditions catalyzed by a rhodium(i)–chiral phosphate system

Augé, Mylène; Barbazanges, Marion; Trần, Anh Tuấn; Simonneau, Antoine; Elley, Paulin; Amouri, Hani; Aubert, Corinne; Fensterbank, Louis; Gandon, Vincent; Malacrìa, Max; Moussa, Jamal; Ollivier, Cyril

doi:10.1039/c3cc43188f

Cited by 36 publications

(13 citation statements)

References 55 publications

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“…Similarly,c ompounds 7ba and 7ca featuring methoxymethoxy and dimethylamino groups, respectively, could also be synthesizedf rom the corresponding compounds 5 and 2a in high yields with 86 % ee.T his asymmetricc atalysis was applicable as well to the enantioselective synthesis of axially chiral9 , 9'-spirobi[benzo[4,5]silolo [2,3-c]pyridine-3,3'(2 H,2'H)-dione] 9 by the reactiono f5c with aryl isocyanates 8. [18] As shown in Equation (2), compounds 9ca and 9cb were obtained with 93 % ee under similarr eaction conditions. The absolute configurationo f9cb was assigned to be S by Xray crystallographic analysis.…”

Section: Resultsmentioning

confidence: 94%

Rhodium‐Catalyzed Synthesis and Optical Properties of Silicon‐Bridged Arylpyridines

Shintani

Misawa

Takano

et al. 2017

Chemistry A European J

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A convergent and regioselective synthesis of silicon-bridged 4-arylpyridines has been developed through a rhodium-catalyzed [2+2+2] cycloaddition of silicon-containing diynes with nitriles. The absorption and emission properties of these compounds have been examined and could be tuned by varying the substituent on the benzene ring, as well as through the protonation or alkylation of the nitrogen atom on the pyridine ring. A catalytic asymmetric synthesis of silicon-centered axially chiral spirocyclic derivatives has also been achieved with high enantioselectivity by using a newly modified MeO-MOP (MeO-MOP=2-(diphenylphosphino)-2'-methoxy-1,1'-binaphthyl) derivative as the chiral ligand. These spirocyclic compounds were found to be CPL-active (CPL=circularly polarized luminescence), representing the first CPL-active compounds based on the chirality at silicon.

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Section: Resultsmentioning

confidence: 94%

Rhodium‐Catalyzed Synthesis and Optical Properties of Silicon‐Bridged Arylpyridines

Shintani

Misawa

Takano

et al. 2017

Chemistry A European J

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“…An original approach, based on the use of chiral counteranions, was recently applied to rhodium-catalyzed [2+2+2] cycloadditions by Aubert, Fensterbank and Ollivier for the synthesis of axially chiral pyridones and represents the first example of atroposelective transformation using asymmetric counteranion-directed catalysis (Table 7.4) [239]. Based on the screening of various diphosphines and chiral silver phosphate salts 142a-e, the best combination for the catalyzed [2+2+2] cycloaddition of a symmetrical 1,6-diyne and a 2-substituted phenyl isocyanate was [Rh(cod)Cl] 2 with dppb (5 mol%) and 7.5 mol% of the chiral silver salt 142a.…”

Section: Rh Catalystsmentioning

confidence: 99%

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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“…[68] The utilization of the corresponding cycloadducts as chiral reagents (P,N ligands and Lewis bases) has been examined. [71] The reactive species is generated in situ from an achiral system based on a dimeric rhodium(I) complex [Rh(cod)Cl] 2 and dppb (diphenylphosphinobutane) in the presence of a chiral silver salt -Ag(S)TRIP -as chloride scavenger. Since 2005, Tanaka and co-workers have reported several approaches to their synthesis under cationic rhodium catalysis conditions, with use either of unsymmetrical 1,6diynes and alkyl isocyanates or of symmetrical diynes and aryl isocyanates.…”

Section: Rhodium 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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Atroposelective [2+2+2] cycloadditions catalyzed by a rhodium(i)–chiral phosphate system

Cited by 36 publications

References 55 publications

Rhodium‐Catalyzed Synthesis and Optical Properties of Silicon‐Bridged Arylpyridines

Rhodium‐Catalyzed Synthesis and Optical Properties of Silicon‐Bridged Arylpyridines

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

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

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