Enantioselective synthesis of chiral acylsilanes by copper/HZNU-Phos-catalyzed asymmetric conjugate addition of diethyzinc to α,β-unsaturated acylsilanes

Lv, Ji-Yuan; Xu, Zheng; Zheng, Zhan‐Jiang; Li, Li; Cui, Yuming; Cao, Jian; Yang, Ke‐Fang; Xu, Li‐Wen

doi:10.1039/c7ra11919d

Cited by 6 publications

(5 citation statements)

References 43 publications

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“…To develop new variants of conjugate addition reaction for the production of enantiopure functional acylsilanes, Xu and co-workers reported a copper-catalyzed conjugate addition of diethylzinc to α,β-unsaturated acylsilanes, which affords various chiral β-functional acylsilanes with moderate to good yields and enantioselectivity in 2017 (Scheme 30). [45] In this work, the multifunctional HZNU-Phos with both a phosphine center and BINOL-based diol moiety was used as a ligand that played a crucial role in the achievement of the best enantioselectivity for this reaction.…”

Section: Some Other Methods For the Synthesis Of Acylsilanesmentioning

confidence: 99%

Recent Advances in the Synthesis of Acylsilanes

Wang

Liu

et al. 2020

ChemCatChem

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Acylsilanes are of wide interest and have been investigated as an important class of organic reaction intermediates with superior chemical and physical properties. Various synthetic methods for the preparation of acylsilanes with mild reaction conditions resulting in excellent yields and high stereoselectiv-ity have been developed. These strategies mainly include stepwise reaction design, oxidative systems, isomerization/rearrangement, silylation of carboxylic acid derivatives and carbonylation. This minireview summarizes recent advances in the synthesis of acylsilanes over the past decade.

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Section: Some Other Methods For the Synthesis Of Acylsilanesmentioning

confidence: 99%

Recent Advances in the Synthesis of Acylsilanes

Wang

Liu

et al. 2020

ChemCatChem

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“…For example, HZNU-Phos ( R a , S c )- 32 efficiently promoted the copper-catalyzed conjugate addition of ZnEt 2 to chalcones. Except for α,β-unsaturated acylsilane, which gave the desired products with moderate ee, all the other 29 examples of aromatic and alkyl α,β-unsaturated ketones we studied gave 75–99% yields of β-ethyl ketones with excellent enantioselectivities (90–99% ee). To the best of our knowledge, the catalytic system exhibited the highest substrate/catalyst ratio (S/C = 20 000) and turnover number (TON = 17 600) for this reaction to date.…”

Section: Modular Strategy For Merging Biaryl Atropisomers With Point ...mentioning

confidence: 99%

Atropisomers with Axial and Point Chirality: Synthesis and Applications

et al. 2022

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Conspectus Enantiopure atropisomers have become increasingly important in asymmetric synthesis and catalysis, pharmaceutical science, and material science since the discovery of inherent features of axial chirality originating from rotational restriction. Despite the advances made in this field to date, it remains highly desirable to construct structurally diverse atropisomers with potentially useful functions. We propose superposition to match axial and point chirality as a potentially useful strategy to access structurally complex and diverse building blocks for organic synthesis and pharmaceutical science because merging atropisomeric backbones with one or more extra chiral elements can topologically broaden three-dimensional environments to create complex scaffolds with multiple tunable parameters. Over the past decade, we have successfully implemented a strategic design for the superposition of axial and point chirality to develop a series of enantiopure atropisomers and have utilized the synergistic functions of these molecules to enhance chirality transfer in various catalytic asymmetric transformations. In this Account, we present several novel atropisomers with superposed axial and point chirality developed in our laboratory. In our studies, this superposition strategy was used to design and synthesize both biaryl and non-biaryl atropisomers from commercially available chiral sources. Consequently, these atropisomers were used to demonstrate the importance of the synergetic functions of axial and point chirality in specific enantioselective reactions. For example, aromatic amide-derived atropisomers, simplified as Xing-Phos arrays, were broadly employed in Ag-catalyzed [3 + 2] cycloaddition by a series of reactions of aldiminoesters with activated alkenes and imines, as well as being used as chiral solvating agents for the discrimination of optically active mandelic acid derivatives. Considering the powerful potential of non-biaryl atropisomers for asymmetric catalysis, we also explored the transition-metal-catalyzed enantioselective construction of a novel backbone of non-biaryl atropisomers (Ar–alkene, Ar–N axis) bearing both axial and point chirality for the design and synthesis of chiral ligands and functional molecules. The studies presented herein are expected to stimulate further research efforts on the development of functional atropisomers by superposition of matching axial and point chirality. In addition to tunable electron and stereohindrance effects, the synergy between matching chiral elements of axial/point chirality and functional groups is proven to be a special function that cannot be ignored for promoting reactivity and chirality-transfer efficiency in enantioselective synthesis. Consequently, our novel types of scaffolds with superposed axial and point chirality that are capable of versatile coordination with various metal catalysts in asymmetric catalysis highlight the power of the superposition of matching axial and point chirality for the construction of synthetically useful atropi...

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“…40 Despite the extensive research conducted on these compounds in the past few decades, [41][42][43] novel methodologies that utilize acylsilanes as powerful reagents in organic chemistry are still being reported. [44][45][46] Experimentally, the use of aromatic acylsilanes is particularly attractive as they do not undergo side reactions involving the carbonyl α-carbon. 47 Moreover, they show an absorption maximum at around 425 nm, thus allowing photoexcitation using visible blue light.…”

Section: Introductionmentioning

confidence: 99%