Convenient Preparation of Silylboranes

Suginome, Michinori; Matsuda, Takanori; Ito, Yoshihiko

doi:10.1021/om000254t

Cited by 189 publications

(131 citation statements)

References 23 publications

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“…Indeed, based on our previous work in the area of transition metalcatalyzed transfer of silicon nucleophiles, [19] we envisaged a new strategy for the preparation of acylsilanes (Scheme 1) through acylation of a copper(I)-silyl intermediate. Starting from type 1 acid derivatives in the presence of Suginomes reagent [20] 2 and a copper catalyst, the process should lead to the corresponding acylsilanes 3.…”

Section: Acylsilanes [Rcosi(r')mentioning

confidence: 99%

Synthesis of Acylsilanes by Copper(I)‐Catalyzed Addition of Silicon Nucleophiles onto Acid Derivatives

Cirriez¹,

Rasson²,

Riant³

2013

Adv Synth Catal

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The transition metal-catalyzed transfer of silicon nucleophiles onto various electrophiles has recently gained considerable attention, due to the now readily available silicon pro-nucleophiles such as silylboronates. Our interest lies in the addition of such species to acid derivatives for the generation of acylsilanes. We report herein an efficient method to synthesize these compounds, starting from easyto-form anhydrides, with very good yields.

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Section: Acylsilanes [Rcosi(r')mentioning

confidence: 99%

Synthesis of Acylsilanes by Copper(I)‐Catalyzed Addition of Silicon Nucleophiles onto Acid Derivatives

Cirriez¹,

Rasson²,

Riant³

2013

Adv Synth Catal

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“…Using thiol ester 1a as the model substrate, various silyl metal reagents 4,8 were tested for ketone synthesis using [PdCl 2 (PPh 3 ) 2 ]. However, silylating reagents, which act as silyl anion sources, did not provide the desired acylsilane (Scheme 3).…”

mentioning

confidence: 99%

Synthesis of Acylsilanes by Palladium-catalyzed Cross-coupling Reaction of Thiol Esters and Silylzinc Chlorides

Azuma¹,

Okano²,

Tokuyama³

2011

Chem. Lett.

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An acylsilane synthesis by a Pd-catalyzed cross-coupling reaction of thiol esters and silylzinc chlorides was developed. S-Phenyl thiol esters with a variety of functional groups were converted to corresponding acylsilanes.Since acylsilanes possess a variety of unique reactivities, 1 their synthesis has been an important research topic in organic chemistry.1p1r,24 Brook 2a and Corey 2b independently reported representative methods to prepare acylsilanes by silylation of a lithiated dithiane followed by removal of dithiane. Acylsilanes are also synthesized by 1,2-addition of silyllithium to aldehydes followed by oxidation according to a procedure of Reich. 5However, both methods have only limited functional group compatibility since they use strong bases such as n-BuLi. To circumvent these problems, palladium-catalyzed cross-coupling of acid chlorides with disilane 4a4d or stannylsilane 4e has recently been reported. These methods, however, are unsatisfactory because they require harsh conditions such as heating at high temperature without solvent. On the other hand, thiol esters are a suitable substrate for cross-coupling reactions based on oxidative addition of a transition-metal catalyst to the CS bond. 6,7 Under this background, we initiated a study of the transformation of thiol esters to acylsilanes. Herein, we report a mild synthesis of acylsilanes by palladium-catalyzed crosscoupling of thiol esters and silylzinc chlorides.Based on the proposed reaction mechanism for the palladium-catalyzed cross-coupling reaction of thiol esters with organozinc reagent (Scheme 1), we considered a working hypothesis for transformation of thiol esters to acylsilanes as shown in Scheme 2. Oxidative addition of palladium(0) to the CS bond of the thiol ester gives acyl palladium species which should be transformed to the acylsilane via transmetalation with a silyl metal reagent followed by reductive elimination with regeneration of Pd(0).With this idea in mind, we explored a suitable silyl metal reagent for the expected cross-coupling reaction. Using thiol ester 1a as the model substrate, various silyl metal reagents 4,8

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“…10 Practical synthesis of (triorganosilyl)pinacolboranes, e.g., (dimethylphenylsilyl)pinacolborane (1c), was achieved by the reaction of triorganosilyllithium with two equivalents of pinacolborane (66) or isopropoxypinacolborane (67) (Scheme 30). 47 This method was applicable to preparation of [(diethylamino)diphenylsilyl]-pinacolborane (1u), in which [(diethylamino)diphenylsilyl]-lithium (68) was used as a silicon reagent (Scheme 31). 48 The diethylamino group on 1u could be converted to a chloro group via reaction with hydrogen chloride to give (chlorodiphenylsilyl)pinacolborane (1v), which allowed reactions with various alcohols in the presence of pyridine to afford (alkoxydiphenylsilyl)pinacolboranes 1i.…”

Section: Preparation Of Silylboranesmentioning

confidence: 99%

Silylboranes as New Tools in Organic Synthesis

Ohmura¹,

Suginome²

2009

Bulletin of the Chemical Society of Japan

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New reactivities of silylboranes are described with their applications to organic synthesis. The silylboranes add to unsaturated organic compounds such as alkynes, alkenes, 1,3-dienes, and allenes in the presence of nickel, palladium, and platinum catalysts. Reactions with isocyanide proceed in the absence of catalysts, giving 1,1-addition products. The silaborations proceed in highly regio-and stereoselective manners, leading to the formation of organic compounds bearing silyl and boryl groups. Silaborations accompanied by regioselective CÍC bond cleavage in three-membered rings take place in the reactions of methylenecyclopropane and vinylcyclopropane derivatives. Unsaturated organic molecules, e.g., 1,3-diene and aldehyde, undergo silaborative CÍC coupling reactions in the presence of transition-metal catalysts. Enantioselective silaboration of terminal allenes and silaborative CÍC cleavage of meso-methylenecyclopropanes have been achieved. Silaborations in which the stereochemical course, i.e., cis and trans stereoselectivities, is governed by the ligand have been established in platinum-catalyzed intramolecular silaborations of alkenes. Synthetic applications of the silaboration products through SuzukiÍMiyaura coupling, one-carbon homologation, oxidation, allylation, and Rhcatalyzed conjugate addition are also described. Synthesis of silylboranes, including those having heteroatom functional groups at the silicon atoms, is summarized.

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Convenient Preparation of Silylboranes

Cited by 189 publications

References 23 publications

Synthesis of Acylsilanes by Copper(I)‐Catalyzed Addition of Silicon Nucleophiles onto Acid Derivatives

Synthesis of Acylsilanes by Copper(I)‐Catalyzed Addition of Silicon Nucleophiles onto Acid Derivatives

Synthesis of Acylsilanes by Palladium-catalyzed Cross-coupling Reaction of Thiol Esters and Silylzinc Chlorides

Silylboranes as New Tools in Organic Synthesis

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