Enantioselective synthesis of <i>gem</i>-diarylalkanes by transition metal-catalyzed asymmetric arylations (TMCAAr)

Jia, Tao; Cao, Ping; Liao, Jian

doi:10.1039/c7sc03404k

Cited by 73 publications

(22 citation statements)

References 106 publications

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“…Transition metal-catalyzed direct functionalization of alkenes has received considerable attention as an efficient method to construct value-added molecular structures through the C–C bond forming reaction . In this field, hydroarylation of styrenes provides a highly straightforward and atom-economical method to the synthesis of 1,1-diarylalkanes that often show biological activity . Generally, two strategies involving the generation of active M–H species have been developed to realize the hydroarylation of alkenes, − in which one strategy undergoes C(sp 2 )–H activation of arenes with a directing group or heteroarenes to form M–H species, and the other method utilizes hydride reagents to form M–H species under reductive conditions.…”

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confidence: 99%

Mechanistic Studies of Nickel-Catalyzed Hydroarylation of Styrenes

Cheng

Dang

2020

Org. Lett.

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The mechanism of nickel-catalyzed hydroarylation of styrenes has been explored with density functional theory. Instead of the stepwise pathway via a Ni(II)–H species, computational results unveil that the concerted RO–H oxidative addition/olefin insertion takes place kinetically favorable to generate the alkylnickel(II) species, which further undergoes transmetalation and reductive elimination to yield the hydroarylated product. The origins of regio- and stereoselectivity were revealed via analyzing the electronic and steric effects of the key transition states.

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confidence: 99%

Mechanistic Studies of Nickel-Catalyzed Hydroarylation of Styrenes

Cheng

Dang

2020

Org. Lett.

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“… 3 The studies on organometallic reagents’ asymmetric conjugate additions of α,β-unsaturated carbonyl compounds have engendered a few reliable catalytic methods. 3 The most outstanding approach among them is the Rh-catalyzed asymmetric conjugate addition of organoboronic acid to α,β-unsaturated carbonyl substrates. 4 , 5 Palladium 6 and copper 7 complexes are also effective catalysts.…”

Section: Introductionmentioning

confidence: 99%

Crown Ether-Derived Chiral BINOL: Enantioselective Michael Addition of Alkenyl Boronic Acids to α,β-Unsaturated Ketones

et al. 2021

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A new class of aza-crown ether-derived chiral BINOL catalysts were designed, synthesized, and applied in the asymmetric Michael addition of alkenylboronic acids to α,β-unsaturated ketones. It was found that introducing aza-crown ethers to the BINOL catalyst could achieve apparently higher enantioselectivity than a similar BINOL catalyst without aza-crown ethers did, although the host–guest complexation of alkali ions by the aza-crown ethers could not further improve the catalysis effectiveness. Under mediation of the aza-crown ether-derived chiral BINOL and in the presence of a magnesium salt, an array of chiral γ,δ-unsaturated ketones were furnished in good enantioselectivities (81–95% ees).

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“…Consequently, the enantioselective synthesis of the 1,1-diarylalkane subunit has become a popular contemporary topic for synthetic organic chemists. [27] Current approaches toward such motifs include asymmetric hydrogenation of 1,1-diarylalkenes, [28,29] , nucleophilic and radical additions to alkenes, [30][31][32] and stereospecific [33][34][35] as well as stereoconvergent [36,37] cross coupling reactions ( Figure 1b). A method that is noticeably absent from this list is a stereoconvergent Suzuki-Miyaura cross coupling reaction.…”

Section: Introductionmentioning

confidence: 99%

An Iron-Based Catalyst Enables The Enantioconvergent Synthesis of Chiral 1,1-Diarylalkanes Through a Suzuki-Miyaura Cross-Coupling Reaction

Tyrol¹,

Yone²,

Gallin³

et al. 2020

Preprint

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By using an iron-based catalyst, access to enantioenriched 1,1-diarylakanes was enabled through an enantioselective Suzuki-Miyaura crosscoupling reaction. The combination of a chiral cyanobis(oxazoline) ligand framework and 1,3,5-trimethoxybenzene additive were essential to afford high yields and enantioselectivities in cross-coupling reactions between unactivated aryl boronic esters and a variety of benzylic chlorides, including challenging ortho-substituted benzylic chloride substrates. Mechanistic investigations implicate a stereoconvergent pathway involving carbon-centered radical intermediates.

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Enantioselective synthesis of gem-diarylalkanes by transition metal-catalyzed asymmetric arylations (TMCAAr)

Abstract: To date, enantiomerically enriched molecules containing gem(1,1)-diaryl containing tertiary or quaternary stereogenic centers have been readily accessed by transition metal-catalyzed enantioselective or stereoconvergent aryl transfer reactions.

Cited by 73 publications

References 106 publications

Mechanistic Studies of Nickel-Catalyzed Hydroarylation of Styrenes

Mechanistic Studies of Nickel-Catalyzed Hydroarylation of Styrenes

Crown Ether-Derived Chiral BINOL: Enantioselective Michael Addition of Alkenyl Boronic Acids to α,β-Unsaturated Ketones

An Iron-Based Catalyst Enables The Enantioconvergent Synthesis of Chiral 1,1-Diarylalkanes Through a Suzuki-Miyaura Cross-Coupling Reaction

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