Functionalized BINOL-<i>mono</i>-PHOS for Multinuclear Cu-Catalysts in Asymmetric Conjugate Addition of Organozinc Reagents

Endo, Kohei; Yakeishi, Sayuri; Hamada, Daisuke; Shibata, Takanori

doi:10.1246/cl.130080

Cited by 18 publications

(4 citation statements)

References 33 publications

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“…In recent years, however, the C 1 ‐symmetric BINOL‐derived ligands and catalysts bearing different functional groups at the 3,3′‐positions (e.g. PPh3 and Bn) have been found to exhibit better enantioinduction toward some transformations than the corresponding C 2 ‐symmetric catalyst (Scheme A) . This observation indicates the C 1 ‐symmetric chiral binaphthyls, that bear different substituents at the 3‐ and 3′‐positions as a “two‐arm” tool to improve stereocontrol, would have great potential in asymmetric catalysis.…”

Section: Methodsmentioning

confidence: 99%

Copper‐Complex‐Catalyzed Asymmetric Aerobic Oxidative Cross‐Coupling of 2‐Naphthols: Enantioselective Synthesis of 3,3′‐Substituted C₁‐Symmetric BINOLs

et al. 2019

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An ovel chiral 1,5-N,N-bidentate ligand based on aspirocyclic pyrrolidine oxazoline backbone was designed and prepared, and it coordinates CuBr in situ to form an unprecedented catalyst that enables efficient oxidative crosscoupling of 2-naphthols.Air serves as an external oxidant and generates as eries of C 1 -symmetric chiral BINOL derivatives with high enantioselectivity (up to 99 %ee) and good yield (up to 87 %). This approach is tolerant of ab roader substrates scope,p articularly substrates bearing various 3-and 3'substituents.Apreliminary investigation using one of the obtained C 1 -symmetric BINOL products was used as an organocatalyst, exhibiting better enantioselectivity than the previously reported organocatalyst, for the asymmetric aalkylation of amino esters.

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Section: Methodsmentioning

confidence: 99%

Copper‐Complex‐Catalyzed Asymmetric Aerobic Oxidative Cross‐Coupling of 2‐Naphthols: Enantioselective Synthesis of 3,3′‐Substituted C₁‐Symmetric BINOLs

et al. 2019

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“…Copper-catalyzed asymmetric conjugate addition of organozinc reagents to enones using functionalized BINOL-mono-PHOS was developed by Endo and Shibata et al (Figure 4a). [31] The reaction was performed in the presence of CuCl (5 mol%) catalyst along with the asymmetric ligand (10 mol%) in THF solvent at À 20 °C. Diethyl-and dimethylzinc were used (3 eq.)…”

Section: Copper-catalyzed Asymmetric Conjugate Additionmentioning

confidence: 99%

Alkylation of Electron‐Deficient Olefins through Conjugate Addition of Organozinc Reagents: An Update

Baruah¹,

Deb

2021

Eur J Org Chem

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This review focuses on the applications of organozinc reagents in conjugate addition reactions. Organozinc compounds are a class of organometallic reagent used in various reactions such as addition, substitution, and coupling reactions. The conjugate addition or 1, 4-addition is one of the most useful bond forming strategies used in organic synthesis since broad range of nucleophiles can be employed in the reaction. Addition of organozinc to electron-deficient olefins attracts synthetic chemists as it preferably undergoes conjugate addition over 1,2addition unlike other organometallic reagents, such as Grignard reagent or organolithium. Many natural products were also synthesized by applying the conjugate addition reaction of organozinc. Moreover, organozinc reagents have superior functional group compatibility and can be easily prepared relative to other organometallic compounds. Consequently, conjugate additions of organozinc reagents were highly studied and having a review on it is very important at present. Though a few reviews are available, they either do not focus directly on the organozinc reagents or not on the conjugate addition. We hope that this review article will be of great use to organic researchers.

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“…In this case, Cu catalysis was employed, with chiral spirocyclic pyrrolidine oxazoline-based ligand (L6) and air as oxidant (Figure 15) [52]. One of the interests in this work was the fact that C1-symmetric BINOL-derived ligands and catalysts bearing different functional groups at the 3,3'-positions (e.g., PPh 3 and Bn) have been shown, in some cases, to display better enantioinduction than the corresponding C2-symmetric catalysts [53]. The catalyst system used in this work was found to be highly chemoselective, as well as to have wide substrate tolerance.…”

Section: Transition Metal-catalyzed Enantioselective Cdcmentioning

confidence: 99%

New Trends in Enantioselective Cross-Dehydrogenative Coupling

2020

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The development of cross-dehydrogenative coupling in recent years has simplified the synthesis of many materials, as a result of facile C–H activation, which, together with its greater atom economy and environmental friendliness, has made an impact on modern organic chemistry. Indeed, many C–C and C–X (X = N, O, P, S, B, or Si) coupling reactions can now be performed directly between two C–H bonds or a C–H and an X–H bond, simply by adding catalytic amounts of a metal salt to a mixture of the two and an oxidant to accept the two hydrogen atoms released. Chiral organocatalysts or chiral ligands have been joined to promote enantioselective processes, resulting in the development of efficient reaction cascades that provide products in high yields and high levels of asymmetric induction through cooperative catalysis. In recent years, photochemical oxidation and electrochemistry have widened even more the scope of cross-dehydrogenative coupling (CDC). In this review, we summarized the recent literature in this subject, hoping that it will inspire many new synthetic strategies.

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Functionalized BINOL-mono-PHOS for Multinuclear Cu-Catalysts in Asymmetric Conjugate Addition of Organozinc Reagents

Cited by 18 publications

References 33 publications

Copper‐Complex‐Catalyzed Asymmetric Aerobic Oxidative Cross‐Coupling of 2‐Naphthols: Enantioselective Synthesis of 3,3′‐Substituted C₁‐Symmetric BINOLs

Copper‐Complex‐Catalyzed Asymmetric Aerobic Oxidative Cross‐Coupling of 2‐Naphthols: Enantioselective Synthesis of 3,3′‐Substituted C₁‐Symmetric BINOLs

Alkylation of Electron‐Deficient Olefins through Conjugate Addition of Organozinc Reagents: An Update

New Trends in Enantioselective Cross-Dehydrogenative Coupling

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Functionalized BINOL-mono-PHOS for Multinuclear Cu-Catalysts in Asymmetric Conjugate Addition of Organozinc Reagents

Cited by 18 publications

References 33 publications

Copper‐Complex‐Catalyzed Asymmetric Aerobic Oxidative Cross‐Coupling of 2‐Naphthols: Enantioselective Synthesis of 3,3′‐Substituted C1‐Symmetric BINOLs

Copper‐Complex‐Catalyzed Asymmetric Aerobic Oxidative Cross‐Coupling of 2‐Naphthols: Enantioselective Synthesis of 3,3′‐Substituted C1‐Symmetric BINOLs

Alkylation of Electron‐Deficient Olefins through Conjugate Addition of Organozinc Reagents: An Update

New Trends in Enantioselective Cross-Dehydrogenative Coupling

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Copper‐Complex‐Catalyzed Asymmetric Aerobic Oxidative Cross‐Coupling of 2‐Naphthols: Enantioselective Synthesis of 3,3′‐Substituted C₁‐Symmetric BINOLs

Copper‐Complex‐Catalyzed Asymmetric Aerobic Oxidative Cross‐Coupling of 2‐Naphthols: Enantioselective Synthesis of 3,3′‐Substituted C₁‐Symmetric BINOLs