Enantioselective Synthesis of 3,3′‐Disubstituted 2‐Amino‐2′‐hydroxy‐1,1′‐binaphthyls by Copper‐Catalyzed Aerobic Oxidative Cross‐Coupling

Zhao, Xiaojing; Li, Duo; Ding, Tong‐Mei; Tian, Jin‐Miao; Tu, Yong‐Qiang; Wang, Aifang; Xie, Yuyang

doi:10.1002/anie.202015001

Cited by 57 publications

(21 citation statements)

References 70 publications

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“…As above, the combination of Ir/CeO 2 and NOBIN is effective for the asymmetric hydrogenation of acetophenone. The synthesis method of NOBIN was reported by Smrcina, Kocovsky, and co-workers in 1992, , and kinetic resolution − and direct chiral coupling of naphthylamine analogues − are developed for the synthesis of chiral NOBIN. There are no reports on the effective combination of heterogeneous catalysts with NOBIN for hydrogenation reactions, while the combination of Ru complexes and NOBIN derivatives was reported to be effective for the transfer hydrogenation of ketones. , …”

Section: Resultsmentioning

confidence: 99%

Heterogeneous Enantioselective Hydrogenation of Ketones by 2-Amino-2′-hydroxy-1,1′-binaphthyl-Modified CeO₂-Supported Ir Nanoclusters

et al. 2021

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Modification of supported noble metals with chiral modifiers is a promising strategy for the design of effective heterogeneous chiral catalysts. The chiral compounds are generally introduced on the surface of noble metals, often leading to low enantioselectivity and to low activity. Herein, a unique heterogeneous chiral catalyst where a chiral modifier is introduced at the interface between the metal cluster and the support is presented. Modification of CeO2-supported Ir nanoclusters with 2-amino-2′-hydroxy-1,1′-binaphthyl (NOBIN) as a chiral modifier provided a heterogeneous chiral catalyst where NOBIN is introduced at the interface between Ir nanoclusters and the CeO2 support. The heterogeneous chiral catalyst enabled the asymmetric hydrogenation of acetophenone to provide 1-phenylethanol with moderate enantiomeric excess (ee) (up to 53%). The catalyst characterizations showed that about 1 nm Ir metal nanoclusters are formed on CeO2, and density functional theory calculations presented that NOBIN is adsorbed onto Ir nanoclusters and CeO2 at the NH2 and OH groups, respectively, constructing the asymmetric reaction field among NOBIN, Ir nanoclusters, and CeO2.

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Section: Resultsmentioning

confidence: 99%

Heterogeneous Enantioselective Hydrogenation of Ketones by 2-Amino-2′-hydroxy-1,1′-binaphthyl-Modified CeO₂-Supported Ir Nanoclusters

et al. 2021

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“…This section discusses the atroposelective arylation methods we pursued by modulating the intrinsic nucleophilicity of arenes to address this reactivity constraint. Considering the limitations of metal-catalyzed oxidative coupling in furnishing non- C 2 -symmetric BINOLs, NOBINs, and BINAMs, early efforts were invested to derive scaffolds with these functional handles.…”

Section: New Synthetic Strategies For Privileged Scaffoldsmentioning

confidence: 99%

Organocatalytic Enantioselective Synthesis of Axially Chiral Molecules: Development of Strategies and Skeletons

Cheng

Xiang²,

Tan³

2022

Acc. Chem. Res.

133

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Metrics & MoreArticle Recommendations CONSPECTUS:The growing importance of axially chiral architectures in different scientific domains has unveiled shortcomings in terms of efficient synthetic access and skeletal variety. This account describes our strategies in answering these challenges within the organocatalytic context where the emergence of bifunctional catalysts such as chiral phosphoric acids (CPAs) has proven invaluable in controlling the sense of axial chirality. The wide occurrence of bi(hetero)aryl skeletons in privileged structures constitutes a strong motivation to devise more effective arylation methods. Our design revolves around modulating the intrinsic nucleophilicity of aromatic amines and alcohols. The first approach involves the design of an electron-withdrawing activating group which could associate with the catalyst for reactivity enhancement and selectivity control. The resonance of arenes offers the unique mechanistic possibility to select between activating sites. C2-Azo-and nitroso-substituted naphthalenes undergo atroposelective ortho C-or N-arylation with (hetero)aromatic nucleophiles. For monocyclic benzenes, programmable charge localization leads to regioselective activation by catalytic control alone or aided by substrate design. For instance, selective addition to nitroso nitrogen enables successive annulation initiated by the amine to yield axially chiral N-arylbenzimidazoles. In a biomimetic manner, a finely tuned catalyst could direct a para-selective nucleophilic approach in the atroposelective arylation of azobenzenes.The second strategy employs electrophilic arene precursors for arylation which occurs via rearomatization with central-to-axial chirality transfer. This enabled the arylation of (imino)quinones with indoles to access phenylindole atropisomers. By adapting this chemistry with an additional oxidation event to liberate the carbonyl functionalities, aryl-o-naphthoquinone and aryl-p-quinone atropisomers were attained. Along with the development of new arylation strategies, deriving new axially chiral structures has been another consistent theme of our research program. The atroposelective functionalization of alkynes provides broad entry to atropisomeric alkenes. The monofunctionalization of alkynes through the interception of an electrophilic vinylidene-quinonemethide (VQM) intermediate with 2-naphthols yielded the new EBINOL scaffolds. By designing an internal directing group, the atroposelective dihalogenation of alkynes was realized using abundant alkali halides despite their weak nucleophilicities and poor solubilities. The atroposelective N-alkylation of alkenes was pursued to prepare multifunctionalized alkene atropisomers that could be converted into 2-arylpyrroles with chirality transfer. The synthesis of B-aryl-1,2-azaborines containing a C−B chiral axis was accomplished where the CPA catalyst effects the desymmetrization and defines the configuration of the distal C−B bond. Inspired by the axially chiral scaffold of allenes, we leveraged the developed aren...

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“…Indeed, since the pioneering work of Kočovský, who synthesized homochiral NOBIN 3 (R = R′ = H) by resolving the racemate with a chiral redox copper amine complex, access to optically pure NOBINs has been limited to enzymatic and chemical resolution methods, stereoselective multistep syntheses, catalytic atroposelective arylation of iminoquinone acetals, and the cross-coupling of 2-naphthols with azonaphthalene derivatives . The first successful oxidative cross-coupling conditions, based on the Cu(I)/SPDO (SPDO = spirocyclic pyrrolidine oxazoline) complex, which provide entry to enantioenriched 3,3′-disubstituted NOBINs, were recently reported by Tian and Tu (Scheme A). ,, Considering the high value of chiral NOBIN scaffolds in organic chemistry, there is an emerging need for their preparation by efficient, general, and direct scalable methods based on earth-abundant inexpensive iron catalysts.…”

Section: Introductionmentioning

confidence: 99%

A Chiral Iron Disulfonate Catalyst for the Enantioselective Synthesis of 2-Amino-2′-hydroxy-1,1′-binaphthyls (NOBINs)

et al. 2022

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A novel type of chiral redox disulfonate iron complex for asymmetric catalysis is reported. The [Fe((R a )-BINSate)] + (BINSate = 1,1′binaphthalene-2,2′-disulfonate) complex effectively promotes the enantioselective oxidative cross-coupling between 2-naphthols (1) and 2-aminonaphthalene derivatives (2), affording optically enriched (R a )-2-amino-2′hydroxy-1,1′-binaphthyls (NOBINs) with exceptional yields and enantioselective ratios (up to 99% yield and 96:4 er). The [Fe((R a )-BINSate)] + catalyst was designed as a chiral version of FeCl 3 with multicoordination sites available for binding the two coupling partners 1 and 2 as well as the oxidant. Our structure−selectivity and activity study, which covered most of the important positions in the NOBIN scaffold, revealed the effect of different substitution patterns on the coupling efficiency and stereoselectivity.

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Enantioselective Synthesis of 3,3′‐Disubstituted 2‐Amino‐2′‐hydroxy‐1,1′‐binaphthyls by Copper‐Catalyzed Aerobic Oxidative Cross‐Coupling

Cited by 57 publications

References 70 publications

Heterogeneous Enantioselective Hydrogenation of Ketones by 2-Amino-2′-hydroxy-1,1′-binaphthyl-Modified CeO₂-Supported Ir Nanoclusters

Heterogeneous Enantioselective Hydrogenation of Ketones by 2-Amino-2′-hydroxy-1,1′-binaphthyl-Modified CeO₂-Supported Ir Nanoclusters

Organocatalytic Enantioselective Synthesis of Axially Chiral Molecules: Development of Strategies and Skeletons

A Chiral Iron Disulfonate Catalyst for the Enantioselective Synthesis of 2-Amino-2′-hydroxy-1,1′-binaphthyls (NOBINs)

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Enantioselective Synthesis of 3,3′‐Disubstituted 2‐Amino‐2′‐hydroxy‐1,1′‐binaphthyls by Copper‐Catalyzed Aerobic Oxidative Cross‐Coupling

Cited by 57 publications

References 70 publications

Heterogeneous Enantioselective Hydrogenation of Ketones by 2-Amino-2′-hydroxy-1,1′-binaphthyl-Modified CeO2-Supported Ir Nanoclusters

Heterogeneous Enantioselective Hydrogenation of Ketones by 2-Amino-2′-hydroxy-1,1′-binaphthyl-Modified CeO2-Supported Ir Nanoclusters

Organocatalytic Enantioselective Synthesis of Axially Chiral Molecules: Development of Strategies and Skeletons

A Chiral Iron Disulfonate Catalyst for the Enantioselective Synthesis of 2-Amino-2′-hydroxy-1,1′-binaphthyls (NOBINs)

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Heterogeneous Enantioselective Hydrogenation of Ketones by 2-Amino-2′-hydroxy-1,1′-binaphthyl-Modified CeO₂-Supported Ir Nanoclusters

Heterogeneous Enantioselective Hydrogenation of Ketones by 2-Amino-2′-hydroxy-1,1′-binaphthyl-Modified CeO₂-Supported Ir Nanoclusters