Synthesis and application of 3‐substituted (<i>S</i>)‐BINOL as chiral ligands for the asymmetric ethylation of aldehydes

Zhang, Zhiguang; Dong, Zhi‐Bing; Li, Jin‐Shan

doi:10.1002/chir.20842

Cited by 23 publications

(2 citation statements)

References 88 publications

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“…The BINOL monoboronic acid was used to make other BINOL derivatives. 111,[254][255][256]338 For example, the Suzuki coupling reaction of (R)-191 was used to prepare bisBINOL compounds such as (R,R)-192. 111 The ortho-lithiated (S)-BINOL-MOM was reacted with 2isopropyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane to give the 3,3′-diboronic ester (R)-193 in 75% yield (Scheme 63).…”

Section: Reactions Of Binol Methoxymethyl Ethermentioning

confidence: 99%

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Regioselective Substitution of BINOL

2024

Chem. Rev.

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1,1′-Bi-2-naphthol (BINOL) has been extensively used as the chirality source in the fields of molecular recognition, asymmetric synthesis, and materials science. The direct electrophilic substitution at the aromatic rings of the optically active BINOL has been developed as one of the most convenient strategies to structurally modify BINOL for diverse applications. High regioselectivity has been achieved for the reaction of BINOL with electrophiles. Depending upon the reaction conditions and substitution patterns, various functional groups can be introduced to the specific positions, such as the 6-, 5-, 4-, and 3-positions, of BINOL. Ortho-lithiation at the 3-position directed by the functional groups at the 2-position of BINOL have been extensively used to prepare the 3- and 3,3′-substituted BINOLs. The use of transition metal-catalyzed C–H activation has also been explored to functionalize BINOL at the 3-, 4-, 5-, 6-, and 7-positions. These regioselective substitutions of BINOL have allowed the construction of tremendous amount of BINOL derivatives with fascinating structures and properties as reviewed in this article. Examples for the applications of the optically active BINOLs with varying substitutions in asymmetric catalysis, molecular recognition, chiral sensing and materials are also provided.

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Section: Reactions Of Binol Methoxymethyl Ethermentioning

confidence: 99%

“… The diboronic acid minor product was removed by column chromatography on silica gel. The BINOL monoboronic acid was used to make other BINOL derivatives. ,− , For example, the Suzuki coupling reaction of ( R )- 191 was used to prepare bisBINOL compounds such as ( R , R )- 192 …”

Section: Ortho-lithiation At 3-positionmentioning

confidence: 99%

Regioselective Substitution of BINOL

2024

Chem. Rev.

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Modular amino acid amide chiral ligands for enantioselective addition of diethylzinc to aromatic aldehydes

Gou

Chang

et al. 2011

Applied Organom Chemis

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Enantioselective addition of diethylzinc to a series of aromatic aldehydes was developed using a modular amino acid amide chiral ligand (2S)-3-phenyl-N-((R)-1-phenyl-ethyl)-2-(tosylamino)propanamide without using titanium complex. The catalytic system employing 10 mol% of 1g was found to promote the addition of diethylzinc (ZnEt 2 ) to a wide range of aromatic aldehydes with electron-donating and electron-withdrawing substituents, giving up to 82% ee of the corresponding secondary alcohol under mild conditions.

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Ar‐BINMOLs with Axial and sp³Central Chirality – Characterization, Chiroptical Properties, and Application in Asymmetric Catalysis

et al. 2011

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Abstract2′‐Hydroxy‐1,1′‐binaphthalene‐2‐(arylmethanol) (Ar‐BINMOLs), a family of new 1,1′‐binaphthalene‐2,2′‐diol derivatives, prepared by a [1,2]‐Wittig rearrangement, are introduced as new chiral molecules for the study of the modes of supramolecular aggregation on the basis of ESI‐MS, NMR spectroscopy, differential scanning calorimetry (DSC), and X‐ray diffractometry. Characterization showed that Ar‐BINMOLs exhibit different characteristics to BINOL and act as supramolecules due to hydrogen bonding and aromatic π–π/C–H···π interactions. In particular, CD measurements of chiral and racemic Ar‐BINMOL 2a in solution and the solid state show a strong Cotton effect, which revealed that amplification of chirality was observed because of the formation of a chiral supramolecular oligomer derived from the racemic monomer. To this end, the Ar‐BINMOLs were used as supramolecular auxiliaries to mediate the Michael reaction of anthrone to (E)‐β‐nitrostyrene and could give the Michael adduct with comparable enantioselectivities. In addition, the Ar‐BINMOLs act as ligands to promote asymmetric 1,2‐addition of diethylzinc to aldehydes, which resulted in excellent yields and enantioselectivities (up to >99.9 % ee) in the reactions of diethylzinc with a broad range of aromatic aldehdyes.

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Synthesis and application of 3‐substituted (S)‐BINOL as chiral ligands for the asymmetric ethylation of aldehydes

Cited by 23 publications

References 88 publications

Regioselective Substitution of BINOL

Regioselective Substitution of BINOL

Modular amino acid amide chiral ligands for enantioselective addition of diethylzinc to aromatic aldehydes

Ar‐BINMOLs with Axial and sp³Central Chirality – Characterization, Chiroptical Properties, and Application in Asymmetric Catalysis

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Synthesis and application of 3‐substituted (S)‐BINOL as chiral ligands for the asymmetric ethylation of aldehydes

Cited by 23 publications

References 88 publications

Regioselective Substitution of BINOL

Regioselective Substitution of BINOL

Modular amino acid amide chiral ligands for enantioselective addition of diethylzinc to aromatic aldehydes

Ar‐BINMOLs with Axial and sp3Central Chirality – Characterization, Chiroptical Properties, and Application in Asymmetric Catalysis

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Ar‐BINMOLs with Axial and sp³Central Chirality – Characterization, Chiroptical Properties, and Application in Asymmetric Catalysis