Asymmetric synthesis of chiral organosilicon compounds via transition metal-catalyzed stereoselective C-H activation and silylation.
TL;DR: In this paper, the progress of transition metal-catalyzed stereoselective sp2 and sp3 C-H activation and silylation in the synthesis of chiral organosilicon compounds is discussed.
About: This article is published in Chemical Communications.The article was published on 2021-08-19. It has received 20 citations till now. The article focuses on the topics: Chiral ligand & Silylation.
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TL;DR: In this paper, the Ni0 -catalyzed ring expansion process was used to obtain enantioenriched silicon-stereogenic benzosiloles with tetraorganosilicon stereocenters in excellent yields and enantioselectivities.
Abstract: The development of a straightforward strategy to obtain enantioenriched silicon-stereogenic benzosiloles remains a challenging yet appealing synthesis venture due to their potential future application in chiral electronic and optoelectronic devices. In this context, all of the existing methods rely on Rh-catalyzed systems and are somewhat limited in scope. Herein, we disclose the first Ni0 -catalyzed ring expansion process that enables the preparation of benzosiloles possessing tetraorganosilicon stereocenters in excellent yields and enantioselectivities. The presented catalysis strategy is further applied to the asymmetric synthesis of silicon-stereogenic bis-silicon-bridged π-extended systems. Preliminary studies reveal that such compounds exhibit fluorescence emission, Cotton effects and circularly polarized luminescence (CPL) activity.
33 citations
25 citations
08 Mar 2022
TL;DR: In this article , the first enantioselective intermolecular C-H silylation of heteroarenes for the synthesis of acyclic silicon-stereogenic heteroarylsilanes was reported.
Abstract: Intermolecular C-H silylation for the synthesis of acyclic silanes bearing silicon-stereogenic center in one enantiomeric form remains unknown to date. Herein, we report the first enantioselective intermolecular C-H silylation of heteroarenes for the synthesis of acyclic silicon-stereogenic heteroarylsilanes. This process undergoes a rhodium-catalyzed direct intermolecular dehydrogenative Si-H/C-H cross-coupling, giving access to a variety of acyclic heteroarylated silicon-stereogenic monohydrosilanes, including bis-Si-stereogenic silanes, in decent yields with excellent chemo -, regio -, and stereo -control, which significantly enlarge the chemical space of the optically active silicon-stereogenic monohydrosilanes.
21 citations
TL;DR: In this paper , Ni-catalyzed chemodivergent reactions of silacyclobutanes with alkynes with a chiral phosphine ligand were demonstrated to be capable of forming silicon-stereogenic allyl vinylsilanes.
Abstract: Transition metal-catalyzed reactions of silacyclobutanes with a variety of π units have attracted much attention and become one of the most straightforward and efficient approaches to rapidly access structurally diverse organosilicon compounds. However, the reaction of silacyclobutanes with alkynes still suffers from some limitations: (1) internal alkynes remain challenging substrates; (2) expensive Pd- or Rh-based catalysts have been employed in all existing systems; (3) controlling chemodivergence has not yet been realized. Herein we realize Ni-catalyzed chemodivergent reactions of silacyclobutanes with alkynes. In comparison with the previous Pd or Rh catalytic systems, our Ni-catalytic system features: 1) complementary substrate scope; 2) ligand-controlled chemodivergence; 3) low cost. The ligand precisely dictates the pathway selectivity, leading to the divergent formation of (benzo)silacyclohexenes and allyl vinylsilanes. Moreover, we demonstrate that employment of a chiral phosphine ligand is capable of forming silicon-stereogenic allyl vinylsilanes in high yields and enantioselectivities. In addition, DFT calculation is performed to elucidate the origin of the switchable selectivities, which is mainly attributed to different ligand steric effects.
16 citations
TL;DR: The first enantioselective construction of silicon-stereogenic silanols via catalytic asymmetric hydrolytic oxidation of dihydrosilanes was reported in this article .
Abstract: Despite a growing progress for the construction of chiral organosilicon compounds, the catalytic asymmetric synthesis of silicon-stereogenic silanols is less explored and remains a considerable challenge. Herein, we report the first enantioselective construction of silicon-stereogenic silanols via catalytic asymmetric hydrolytic oxidation of dihydrosilanes. This practical protocol features ambient reaction conditions, high atom economy, good functional-group compatibility, and cleaner manner with H2 as the only by-product, producing a wide range of valuable chiral silanols and bis-silanols in decent yields with excellent chemo- and stereoselectivity.
12 citations
References
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TL;DR: The fundamental principles that govern the reactivity of intermediates containing metal-boron bonds are emphasized and how an understanding of the effects of the ligands on this reactivity led us to broaden the scope of main group reagents that react under mild conditions to generate synthetically useful organosilanes is described.
Abstract: Methods that functionalize C–H bonds can lead to new approaches for the synthesis of organic molecules, but to achieve this goal, researchers must develop site-selective reactions that override the inherent reactivity of the substrates. Moreover, reactions are needed that occur with high turnover numbers and with high tolerance for functional groups if the C–H bond functionalization is to be applied to the synthesis of medicines or materials. This Account describes the discovery and development of the C–H bond functionalization of aliphatic and aromatic C–H bonds with borane and silane reagents. The fundamental principles that govern the reactivity of intermediates containing metal–boron bonds are emphasized and how an understanding of the effects of the ligands on this reactivity led us to broaden the scope of main group reagents that react under mild conditions to generate synthetically useful organosilanes is described.Complexes containing a covalent bond between a transition metal and a three-coordina...
804 citations
TL;DR: This Review documents recent advances in asymmetric catalysis, with special emphasis on the most innovative asymmetric processes and the development of novel, efficient types of ferrocene ligands.
Abstract: Despite the impressive progress achieved in asymmetric catalysis during the last decade, an increasing number of new catalysts, ligands, and applications are reported every year to satisfy the need to embrace a wider range of reactions and to improve the efficiency of existing processes. Because of their availability, unique stereochemical aspects, and wide variety of coordination modes and possibilities for the fine-tuning of the steric and electronic properties, ferrocene-based ligands constitute one of the most versatile ligand architectures in the current scenario of asymmetric catalysis. Over the last few years ferrocene catalysts have been successfully applied in an amazing variety of enantioselective processes. This Review documents these recent advances, with special emphasis on the most innovative asymmetric processes and the development of novel, efficient types of ferrocene ligands.
651 citations
TL;DR: Applications such as inhibitor design, imaging, drug release technology, and mapping inhibitor binding are discussed.
Abstract: The incorporation of silicon and synthesis of organosilicon small molecules provide unique opportunities for medicinal applications. The biological investigation of organosilicon small molecules is particularly interesting because of differences in their chemical properties that can contribute to enhanced potency and improved pharmacological attributes. Applications such as inhibitor design, imaging, drug release technology, and mapping inhibitor binding are discussed.
634 citations
TL;DR: This tutorial review classifies various organosilicon reagents depending on substituents on silicon and surveys their cross-coupling reactions with various electrophiles.
Abstract: Much attention has been paid to the cross-coupling reaction of organosilicon compounds due to their stability, non-toxicity, and natural abundance of silicon. In addition, the silicon-based cross-coupling has many advantages over other cross-coupling protocols. Successful examples of the silicon-based cross-coupling reaction are reviewed, focusing especially on the advances made in the last decade. Having had a number of highly effective palladium catalysts developed mainly for other cross-coupling reactions, the development of the silicon-based protocol owes heavily to the design of organosilicon reagents which effectively undergo transmetalation, a key elemental step of the silicon-based cross-coupling reaction. This tutorial review thus classifies various organosilicon reagents depending on substituents on silicon and surveys their cross-coupling reactions with various electrophiles.
539 citations
TL;DR: The advantages of using ferrocene as a scaffold for chiral ligands are described, particularly those regarding planar chirality, rigid bulkiness, and ease of derivatization.
Abstract: Chiral ferrocene ligands have been widely used in asymmetric catalysis. The advantages of using ferrocene as a scaffold for chiral ligands are described, particularly those regarding planar chirality, rigid bulkiness, and ease of derivatization. The role of planar chirality in 1,2- and 1,1￠-disubstituted ferrocene systems is discussed. By using a bulky ferrocene fragment, novel ferrocene ligands were designed, and high enantioselectivity and regioselectivity were achieved in the allylic substitution reaction of monosubstituted allyl substrates. Using the tunable electronic properties of a diphosphine-oxazoline ferrocenyl ligand, the regioselectivity of the intermolecular asymmetric Heck reaction was also examined.
503 citations