Reaction of acylsilanes with α-sulfinyl carbanions: regioselective synthesis of silyl enol ethers

Honda, M.; Nakajima, Tadashi; Okada, Maiko; Yamaguchi, Keita; Suda, Mitsuhiro; Kunimoto, Ko‐Ki; Segi, Masahito

doi:10.1016/j.tetlet.2011.05.041

Cited by 20 publications

(10 citation statements)

References 18 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…He has used the sulfinyl-allylic alcohols obtained in the addition of lithium-vinylsulfoxides to aldehydes in oxidation studies [69][70][71][72], isomerization reactions [73], and Overman [74], Claisen [75], and sulfoxide-sulfenate [76] rearrangements. In addition, Honda and coworkers [80] have published the addition of lithium vinylsulfoxides to acyl silanes, providing in this manner regioselective silyl allene derivatives (Equation b, Scheme 8.17). This is a double asymmetric induction process where the matched pair is conformed by the reagents of the opposite configuration (right, Scheme 8.16), giving the allylic amine derivative with excellent diastereoselectivity and good yields.…”

Section: Vinylic Carbanionsmentioning

confidence: 99%

Sulfur‐Bearing Lithium Compounds in Modern Synthesis

Ruano

Parra

Alemán

2014

Lithium Compounds in Organic Synthesis

View full text Add to dashboard Cite

Sulfur functions have been widely used for the stabilization of lithium carbanions. Their different oxidation states determine a variety of mechanisms for such stabilization, mainly related with their electronic effects (−I and −M) and associative abilities and also with the relative position of sulfur with respect to the C-Li bond. As additional interest, the sulfur of some of these functions is a stable stereogenic center, and their interactions with prochiral lithium carbanions are able to control the stereochemical course of their reactions with electrophiles, which can be successfully used in asymmetric synthesis. Finally, the chemical versatility of the sulfur functions and their easy elimination under diverse conditions confer to the sulfur-stabilized lithium carbanions a very important role in modern synthetic chemistry. In this chapter, we have organized the information attending to the relative position of the carbanionic center with respect to the sulfur function (α-, β-, and γ-lithiation, see Figure 8.1). Each item has been subdivided according to the nature of the sulfur function stabilizing the carbanion. In this sense, sulfoxides, sulfones, and sulfoximines are the three main functions stabilizing any type of lithium-carbanions, but the thioethers have also been described as stabilizing in αand β-lithiation processes. The fragment connecting S and Li is always formed by carbon atoms, but N is present in some cases of γ-lithiation.This chapter covers the literature of the last 10-12 years concerning the preparation and main synthetic applications of the lithium carbanions stabilized by sulfur functions. In most of the cases, the information that appeared in this century helps understand the role of the sulfur functions in the stabilization of the lithium carbanions, and therefore we have only mentioned, as introduction, the seminal references in the field. However, in those cases where there are few references in the last decade and most of the information has been reported before 2000, we have included and briefly commented on the most significant contributions to be able to understand the interest of such stabilizing functions. During the last decade have appeared excellent revisions concerning the reactivity and structure of lithium carbanions [1], the use of different sulfur functions in asymmetric synthesis [2], as Lithium Compounds in Organic Synthesis: From Fundamentals to Applications, First Edition. Edited by Renzo Luisi and Vito Capriati.

show abstract

Section: Vinylic Carbanionsmentioning

confidence: 99%

Sulfur‐Bearing Lithium Compounds in Modern Synthesis

Ruano

Parra

Alemán

2014

Lithium Compounds in Organic Synthesis

View full text Add to dashboard Cite

show abstract

“…Acylsilanes or α-silyl ketones have been known as a unique class of silicon compounds [1][2][3][4][5][6][7][8][9], showing remarkably red-red shifted n→π* transition bands [1,2] and being useful as distinct reagents in organic synthesis [4][5][6][10][11][12][13][14][15][16][17][18][19]. Most of all, acyltris(trimethylsilyl)silanes are of particular importance, which were utilized for the synthesis of the first stable silicon-carbon doubly bonded compounds (silenes) [20,21].…”

Section: Introductionmentioning

confidence: 99%

Reactions of an Isolable Dialkylsilylene with Aroyl Chlorides. A New Route to Aroylsilanes

et al. 2016

View full text Add to dashboard Cite

Abstract:The reactions of isolable dialkylsilylene 1 with aromatic acyl chlorides afforded aroylsilanes 3a-3c exclusively. Aroylsilanes 3a-3c were characterized by 1 H-, 13 C-, and 29 Si-NMR spectroscopy, high-resolution mass spectrometry (HRMS), and single-crystal molecular structure analysis. The reaction mechanisms are discussed in comparison with related reaction of 1 with chloroalkanes and chlorosilanes.

show abstract

“…Thus, we decided to target ArCH 2 SiMe 3 products since they are stable and offer various options for subsequent transformations (Scheme 2) and are at the same time inert towards common cross-coupling catalysts. [13][14][15][16][17][18][19][20] With these considerations in mind we began to evaluate MCH 2 SiMe 3 nucleophiles in the presence of readily available nickel catalysts. Grignard reagents of the XMgCH 2 SiMe 3 type showed reduced reactivity because of the trimethylsilane (TMS) functionality.…”

mentioning

confidence: 99%

“…The oxidation to acyl silanes extends the scope and allows the synthesis of further alcohols, aldehydes, ketones, esters, and acetals as well as other diverse structural elements. [18][19][20] In summary, a new method has been introduced which allows direct replacement of aromatic methoxy groups with bifunctional nucleophiles. Synthetically, this can be achieved in a one-step nickel-catalyzed reaction of aryl ethers, whereby the products are obtained in good yields under mild reaction conditions.…”

mentioning

confidence: 99%

Metal‐Catalyzed Dealkoxylative C_arylC Cross‐Coupling—Replacement of Aromatic Methoxy Groups of Aryl Ethers by Employing a Functionalized Nucleophile

et al. 2014

View full text Add to dashboard Cite

The direct replacement of aromatic methoxy groups with activated carbon nucleophiles would give rise to novel synthetic pathways for targeted and diversity-oriented syntheses. We demonstrate here that this transformation can be achieved in a one-step reaction involving a bifunctional organolithium nucleophile in combination with a CAr OMe bond-cleaving nickel catalyst. The resulting products are stable, α-CH active, and suitable for various further modifications.

show abstract

Reaction of acylsilanes with α-sulfinyl carbanions: regioselective synthesis of silyl enol ethers

Cited by 20 publications

References 18 publications

Sulfur‐Bearing Lithium Compounds in Modern Synthesis

Sulfur‐Bearing Lithium Compounds in Modern Synthesis

Reactions of an Isolable Dialkylsilylene with Aroyl Chlorides. A New Route to Aroylsilanes

Metal‐Catalyzed Dealkoxylative C_arylC Cross‐Coupling—Replacement of Aromatic Methoxy Groups of Aryl Ethers by Employing a Functionalized Nucleophile

Contact Info

Product

Resources

About

Reaction of acylsilanes with α-sulfinyl carbanions: regioselective synthesis of silyl enol ethers

Cited by 20 publications

References 18 publications

Sulfur‐Bearing Lithium Compounds in Modern Synthesis

Sulfur‐Bearing Lithium Compounds in Modern Synthesis

Reactions of an Isolable Dialkylsilylene with Aroyl Chlorides. A New Route to Aroylsilanes

Metal‐Catalyzed Dealkoxylative CarylC Cross‐Coupling—Replacement of Aromatic Methoxy Groups of Aryl Ethers by Employing a Functionalized Nucleophile

Contact Info

Product

Resources

About

Metal‐Catalyzed Dealkoxylative C_arylC Cross‐Coupling—Replacement of Aromatic Methoxy Groups of Aryl Ethers by Employing a Functionalized Nucleophile