Chiral Bidentate NHC Ligands Based on the 1,1′‐Binaphthyl Scaffold: Synthesis and Application in Transition‐Metal‐Catalyzed Asymmetric Reactions

Xu, Qin; Gu, Peng; Jiang, Hanchun; Wei, Yin; Shi, Min

doi:10.1002/tcr.201600103

Cited by 9 publications

(6 citation statements)

References 82 publications

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“…The two central Au(I) cations exhibit nearly linear complexing modes, with two C MIC –Au(I)–Cl angles ranged from 176.15 to 179.39°. The Au–C MIC bonds ranged from 1.986(0) to 2.032(8) Å, which is similar to the previous reported Au(I)–C bond length. − In complexes ( R )- 8a , ( R )- 8f , and ( R )- 8g , the distances between the two auric cations ranged from 4.830(6) to 5.365(6) Å, without Au(I)–Au(I) interaction.…”

Section: Resultssupporting

confidence: 86%

“…As shown in Table , the 13 C NMR spectrum of complexes ( R )- 8a – g display the characteristic resonance at the region 158–161 ppm, which are corresponding to the Au–C MIC moiety (Table ). − The bis(MIC)-bis(Au) structures of ( R )- 8a could be deduced from their high-resolution mass spectrometry {HRMS (ESI) for [C 38 H 28 Au 2 ClN 6 ] + , calcd: 997.1401. Found: 997.1430}, which correspond to [Au 2 LCl] + .…”

Section: Resultsmentioning

confidence: 99%

“…In 2011, an axially chiral N -heterocyclic carbene gold(I) complex was developed by Shi’s group and was applied in 1,6-enyne’s asymmetric cycloisomerization reaction (Scheme B) . Thereafter, a variety of axially chiral NHC–Au(I) complexes, which contained different ligands, including imidazol-2-ylidenes, 1,2,4-triazol-5-ylidenes, and diaminocarbenes, have been developed by the groups of Kündig, Shi, Mascareñas, Espinet, Toste, ,, and Slaughter (Scheme A,B) . Specifically, Toste’s group recently reported a chiral NHC bearing Au(III) catalyst to catalyze 1,5-enyne’s enantioconvergent kinetic resolution (Scheme C) …”

Section: Introductionmentioning

confidence: 99%

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Synthesis of Axially Chiral 1,2,3-Triazol-5-ylidene–Au(I) Complex and Its Application in Enantioselective [2 + 2] Cycloaddition of Alleneamides with Alkenes

et al. 2018

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A series of axially chiral bis-1,2,3-triazol-5-ylidene Au(I) complexes (R)-8a–g and one mono-1,2,3-triazol-5-ylidene Au(I) complex (R)-9a were prepared from commercially available (R)-binaphthyl-2,2-diamine (BINAM) compound, in which, transmetalation of bis(MIC)-bis[Ag(I)] intermediates to the corresponding Au(I) complexes were employed as the key synthetic step. The structures of these MIC–Au(I) complexes were diversified by using different alkyne reagents in copper catalyzed azide–alkyne cycloaddition (CAAC) step. Three chiral bis-1,2,3-triazol-5-ylidene Ag(I) complexes, (R)-7a, (R)-7c, and (R)-7d, were prepared and fully characterized. On the basis of (R)-7a’s crystal structure, a chiral tetra(MIC)-bis(Ag) structure was exhibited, with two chiral bis-1,2,3-triazol-5-ylidene ligands interconnected by two nearly linear silver atom bridges, of which, significant Ag(I)–Ag(I) bonding existed. The crystal structures of (R)-8a, (R)-8f, and (R)-8g were also obtained, which exhibit an axially chiral bis(MIC)-bis(Au) structure without Au(I)–Au(I) interaction. Application of these axially chiral bis-/mono- 1,2,3-triazol-5-ylidene Au(I) complexes in the enantioselective [2 + 2] cycloaddition of alleneamides 10a with p-methoxy styrene 11a were explored, in which (R)-8b with p-methoxy phenyl substituent performed better than other Au(I) complexes. Various substrate scopes, including different alleneamides and mono-, bisubstituted olefins were investigated by using (R)-8b/AgSbF6 catalyst combination. It was found that product’s enantioselectivities are highly dependent upon substrate’s structure, especially in the reactions of acyclic allenesulfoamide substrates. Most of the chiral cyclobutane product’s enantioselectivities ranged from 61 to 99% ee. The [2 + 2] cycloaddition of 2,3-dimethylindole 13 with alleneamide 10a was also explored by using (R)-8b and (R)-8g as the catalyst precursors.

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Section: Resultssupporting

confidence: 86%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Synthesis of Axially Chiral 1,2,3-Triazol-5-ylidene–Au(I) Complex and Its Application in Enantioselective [2 + 2] Cycloaddition of Alleneamides with Alkenes

et al. 2018

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“…1,1′-Binaphthyl-2,2′-diol is a chiral organic compound that is often used as a ligand for transition-metal catalyzed asymmetric synthesis [34,35]. Unlike traditional high-activity bisphenol monomers that have been used for condensation polymerization to make poly(arylene ether)s, the rigid 1,1′-binaphthyl-2,2′-diol has a pair of phenol groups facing to each other within a short spacing, yielding high steric hindrance for the complete SN 2 substitution of the phenol groups.…”

Section: Introductionmentioning

confidence: 99%

Sulfonated Binaphthyl-Containing Poly(arylene ether ketone)s with Rigid Backbone and Excellent Film-Forming Capability for Proton Exchange Membranes

Zhang

Chen

et al. 2018

Polymers

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Sterically hindered (S)-1,1′-binaphthyl-2,2′-diol had been successfully copolymerized with 4,4′-sulfonyldiphenol and 4,4′-difluorobenzophenone to yield fibrous poly(arylene ether ketone)s (PAEKs) containing various amounts of binaphthyl unit, which was then selectively and efficiently sulfonated using ClSO3H to yield sulfonated poly(arylene ether ketone)s (SPAEKs) with ion exchange capacities (IECs) ranging from 1.40 to 1.89 mmol·g−1. The chemical structures of the polymers were confirmed by 2D 1H–1H COSY NMR and FT-IR. The thermal properties, water uptake, swelling ratio, proton conductivity, oxidative stability and mechanical properties of SPAEKs were investigated in detail. It was found that the conjugated but non-coplanar structure of binaphthyl unit endorsed excellent solubility and film-forming capability to SPAEKs. The SPAEK-50 with an IEC of 1.89 mmol·g−1 exhibited a proton conductivity of 102 mS·cm−1 at 30 °C, much higher than that of the state-of-the-art Nafion N212 membrane and those of many previously reported aromatic analogs, which may be attributed to the likely large intrinsic free volume of SPAEKs created by the highly twisted chain structures and the desirable microscopic morphology. Along with the remarkable water affinity, thermal stabilities and mechanical properties, the SPAEKs were demonstrated to be promising proton exchange membrane (PEM) candidates for potential membrane separations.

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“…Various substituted 1,1′‐binaphthyl‐based NHC ligands have been used to ligate with late transition metals especially, ruthenium, palladium and nickel to access a library of chiral catalysts, which can act as excellent chiral induction agents . In 2016, Shi and co‐workers reviewed the use of NHC complexes derived from this particular scaffold and their applications in asymmetric catalysis …”

Section: Au(i)‐carbene Complexes Of Chiral Nhc Ligandsmentioning

confidence: 99%

Coinage Metal Complexes of Chiral N‐Heterocyclic Carbene Ligands: Syntheses and Applications in Asymmetric Catalysis

et al. 2020

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Chiral N‐heterocyclic carbenes (NHCs) have become ligands of choice due to their remarkable catalytic activity in organic transformation reactions. Combining the chiral NHC ligand family and coinage metals became a productive area of research. The organometallic chemistry of coinage metals with the chiral N‐heterocyclic carbene (NHC) ligands is reviewed, with a special emphasis on the synthesis, characterization and possible applications obtained. Significant sections are devoted to the various recently developed coinage metal‐chiral NHC complexes and a detailed comparison of their activities which aims to rationalize the structure–activity relationships. Various methods of preparations of coinage metal‐chiral NHC complexes along with some typical examples of reactivity and mechanisms are covered. Cu‐chiral NHC complexes involved in conjugated additions, allylic substitutions, boration of alkenes, hydrosilylation of ketones and formation of alkenes are covered, along with some remarkable examples and reactivity of Ag‐chiral NHC complexes. Finally, applications of Au‐chiral NHC complexes in the asymmetric cyclization of ester‐functionalized 1,6‐enynes, 1,6‐enyneamines and substituted propargyloxymethanes are also reviewed.

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Chiral Bidentate NHC Ligands Based on the 1,1′‐Binaphthyl Scaffold: Synthesis and Application in Transition‐Metal‐Catalyzed Asymmetric Reactions

Cited by 9 publications

References 82 publications

Synthesis of Axially Chiral 1,2,3-Triazol-5-ylidene–Au(I) Complex and Its Application in Enantioselective [2 + 2] Cycloaddition of Alleneamides with Alkenes

Synthesis of Axially Chiral 1,2,3-Triazol-5-ylidene–Au(I) Complex and Its Application in Enantioselective [2 + 2] Cycloaddition of Alleneamides with Alkenes

Sulfonated Binaphthyl-Containing Poly(arylene ether ketone)s with Rigid Backbone and Excellent Film-Forming Capability for Proton Exchange Membranes

Coinage Metal Complexes of Chiral N‐Heterocyclic Carbene Ligands: Syntheses and Applications in Asymmetric Catalysis

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