Highly Diastereoselective Addition of Lithio Vinyl Sulfoxides to <i>N</i>-Sulfinimines: An Entry to Enantiopure 3-Sulfinyl-2,5-<i>cis</i>-dihydropyrroles

Viso, Alma; Pradilla, Roberto Fernández de la; Ureña, Mercedes; Colomer, Ignacio

doi:10.1021/ol801878f

Cited by 29 publications

(12 citation statements)

References 47 publications

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“…25-2.35 (m, 4H,C H 2 piperidine + H-1), 2.59 (m, 2H,C H 2 piperidine), 4. 15 (m, 1H,H -2), 5.13 (d, 1H, J = 6.1 5. 61 (ddd, 1H, J = 15.3, 6.1, 1.1 Hz, H-3), 5.81 (ddd,1H,J = 15.4,6.1,1.0 Hz,1H,P h),4H,Ph); 13 CNMR (CDCl 3 ,1 25 MHz): d = 13.7 (3 x CH 2 nBu), 13.8 (3 x CH 3 nBu), 24.1 (CH 2 piperidine), 25.4 (3 x CH 2 nBu), 25.9 (2 x CH 2 piperidine), 26.6 (3 x CH 2 nBu), 54.5 (2 x CH 2 piperidine), 64.4 (C-1), 66.7 (C-2), 74.8 (C-5), 126.1 (2 x Ph), 127.0 (Ph), 128.1 (2 x Ph), 129.7 (C-3), 135.2 (C-4), 143. 8 (Ph).…”

Section: Methodsmentioning

confidence: 99%

“…In connection with our interest in the development of stereocontrolled methodologies using enantiopure sulfinyl auxiliaries, [5] and our interesti na cyclic stereocontrol,w ec onsidered that functionalized sulfinyl dienes A could undergo ac onjugate addition of an appropriate nucleophile, [6] to generate intermediate B (Scheme 1b). Subsequent protonation, either to alkenyl sulfoxides B' with ensuing isomerization, or to allylic sulfoxides C,c ontrolled by the preexisting contiguous chiral center,w ould eventually trigger the highly selective [ 2,3]-sigmatropic rearrangementt op roduce unsaturated 1,4-diol or 1,4-aminoalcohold erivatives D,a fter sulfenate cleavage by excess nucleophile acting as thiophile.…”

Section: Introductionmentioning

confidence: 99%

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Sulfinyl‐Mediated Stereoselective Functionalization of Acyclic Conjugated Dienes

Colomer

Ureña

Viso

et al. 2020

Chemistry A European J

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The chemo‐ and stereocontrolled functionalization of conjugated sulfinyl dienes in a cascade process that involves a conjugate addition, diastereoselective protonation and a [2,3]‐sigmatropic rearrangement is reported. Enantioenriched 1,4‐diol and 1,4‐aminoalcohol derivatives are obtained in a very straightforward manner. Further functionalization of these structures, including highly stereoselective epoxidation, dihydroxylation and the stereodivergent synthesis of several polyols in a controlled fashion is described.

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Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Sulfinyl‐Mediated Stereoselective Functionalization of Acyclic Conjugated Dienes

Colomer

Ureña

Viso

et al. 2020

Chemistry A European J

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“…[115][116][117] Viso et al demonstrated stereoselective synthesis of enantiopure dihydropyrroles where TBATB plays the dual role of brominating agent as well as an acid catalyst. 118,119 Here, the double bond functionality first undergoes bromination to form the dibromo intermediate in the presence of the brominating reagent TBATB. Next TBATB catalyses the reaction to undergo base induced bromo-cyclization (Scheme 35).…”

Section: Synthesis Of Enantiopure Dihydropyrroles From a Sulfinylsulf...mentioning

confidence: 99%

Synthetic utility of biomimicking vanadium bromoperoxidase and n-tetrabutylammonium tribromide (TBATB) in organic synthesis

et al. 2022

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“…Moreover, Satoh and coworkers [66][67][68] prepared different bioactive products from the 1-chlorovinyl ptolylsulfoxide, resulting in the addition of α-chlorosulfinyl carbanions to aldehydes and further elimination with MsCl. In 2008, Viso and Fernández de la Pradilla [77,78] published the first addition of sulfinylated vinyl carbanions to N-sulfinyl-imines. 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.…”

Section: Vinylic Carbanionsmentioning

confidence: 99%

Sulfur‐Bearing Lithium Compounds in Modern Synthesis

Ruano

Parra

Alemán

2014

Lithium Compounds in Organic Synthesis

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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.

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Highly Diastereoselective Addition of Lithio Vinyl Sulfoxides to N-Sulfinimines: An Entry to Enantiopure 3-Sulfinyl-2,5-cis-dihydropyrroles

Cited by 29 publications

References 47 publications

Sulfinyl‐Mediated Stereoselective Functionalization of Acyclic Conjugated Dienes

Sulfinyl‐Mediated Stereoselective Functionalization of Acyclic Conjugated Dienes

Synthetic utility of biomimicking vanadium bromoperoxidase and n-tetrabutylammonium tribromide (TBATB) in organic synthesis

Sulfur‐Bearing Lithium Compounds in Modern Synthesis

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