Kinetic Resolution of Axially Chiral 2‐Amino‐1,1′‐Biaryls by Phase‐Transfer‐Catalyzed N‐Allylation

Shirakawa, Seiji; Wu, Xia; Maruoka, Keiji

doi:10.1002/anie.201308237

Cited by 119 publications

(35 citation statements)

References 81 publications

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“…To the best of our knowledge, this is the first successful example of the catalytic enantioselective synthesis of 2‐amino‐2′‐thio axially chiral compounds . Importantly, this amino sulfide is a privileged scaffold and can serve as a platform molecule (Scheme c): i) It is a precursor of potential (S,N)‐ligands and ‐catalysts.…”

Section: Figurementioning

confidence: 99%

Enantioselective Construction of Axially Chiral Amino Sulfide Vinyl Arenes by Chiral Sulfide‐Catalyzed Electrophilic Carbothiolation of Alkynes

Liang¹,

Ji²,

Zhang³

et al. 2020

Angew Chem Int Ed

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The enantioselective construction of axially chiral compounds by electrophilic carbothiolation of alkynes is disclosed for the first time. This enantioselective transformation is enabled by the use of a Ts‐protected bifunctional sulfide catalyst and Ms‐protected ortho‐alkynylaryl amines (Ts=tosyl; Ms=mesyl). Both electrophilic arylthiolating and electrophilic trifluoromethylthiolating reagents are suitable for this reaction. The obtained products of axially chiral vinyl–aryl amino sulfides can be easily converted into biaryl amino sulfides, biaryl amino sulfoxides, biaryl amines, vinyl–aryl amines, and other valuable difunctionalized compounds.

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Section: Figurementioning

confidence: 99%

Enantioselective Construction of Axially Chiral Amino Sulfide Vinyl Arenes by Chiral Sulfide‐Catalyzed Electrophilic Carbothiolation of Alkynes

Liang¹,

Ji²,

Zhang³

et al. 2020

Angew Chem Int Ed

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“…An efficient approach towards the kinetic resolution of axially chiral 2‐amino‐1,1′‐biaryls by a phase‐transfer‐catalyzed N ‐allylation method has been reported (Scheme ) 43. Maruoka and co‐workers proposed that a phase‐transfer catalyst might directly interact with axially chiral amino compounds by the formation of an ion pair, which may facilitate the efficient chiral recognition of the amino compound.…”

Section: Catalytic Kinetic Resolutionsmentioning

confidence: 99%

Catalytic Kinetic Resolution of Biaryl Compounds

Sibi

2015

Chemistry A European J

168

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Biaryl compounds with axial chirality are very common in synthetic chemistry, especially in catalysis. Axially chiral biaryls are important due to their biological activities and extensive applications in asymmetric catalysis. Thus the development of efficient enantioselective methods for their synthesis has attracted considerable attention. This Minireview discusses the progress made in catalytic kinetic resolution of biaryl compounds and chronicles significant advances made recently in catalytic kinetic resolution of biaryl scaffolds.

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“…Recently an umber of catalytic methods have been reportedf or the kinetic resolution (KR) [6] of O-and/or N-protected BINOL and NOBIN derivatives [7] using enzymes, [8] transition metals, [9] and organocatalysts. [10] Despite this interest, small molecule Lewis base catalysed acylative KRs of these substrates has not been widely explored. [11] Sibi has reported the acylative KR of mono-protected biaryl diols using af luxionally chiral DMAP catalyst with moderate to good selectivity factors [12] (Scheme 1a, s = 10-50), [13] however the KR of unprotected chiral biaryl diols remains surprisingly underdeveloped.…”

Section: Introductionmentioning

confidence: 99%

Isothiourea‐Catalysed Regioselective Acylative Kinetic Resolution of Axially Chiral Biaryl Diols

Greenhalgh

Smith

2019

Chemistry A European J

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An operationally simple isothiourea‐catalysed acylative kinetic resolution of unprotected 1,1′‐biaryl‐2,2′‐diol derivatives has been developed to allow access to axially chiral compounds in highly enantioenriched form (s values up to 190). Investigation of the reaction scope and limitations provided three key observations: i) the diol motif of the substrate was essential for good conversion and high s values; ii) the use of an α,α‐disubstituted mixed anhydride (2,2‐diphenylacetic pivalic anhydride) was critical to minimize diacylation and give high selectivity; iii) the presence of substituents in the 3,3′‐positions of the diol hindered effective acylation. This final observation was exploited for the highly regioselective acylative kinetic resolution of unsymmetrical biaryl diol substrates bearing a single 3‐substituent. Based on the key observations identified, acylation transition state models have been proposed to explain the atropselectivity of this kinetic resolution.

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Kinetic Resolution of Axially Chiral 2‐Amino‐1,1′‐Biaryls by Phase‐Transfer‐Catalyzed N‐Allylation

Cited by 119 publications

References 81 publications

Enantioselective Construction of Axially Chiral Amino Sulfide Vinyl Arenes by Chiral Sulfide‐Catalyzed Electrophilic Carbothiolation of Alkynes

Enantioselective Construction of Axially Chiral Amino Sulfide Vinyl Arenes by Chiral Sulfide‐Catalyzed Electrophilic Carbothiolation of Alkynes

Catalytic Kinetic Resolution of Biaryl Compounds

Isothiourea‐Catalysed Regioselective Acylative Kinetic Resolution of Axially Chiral Biaryl Diols

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