An Approach to the Stereoselective Synthesis of Enantiopure Dihydropyrroles and Aziridines from a Common Sulfinyl-Sulfinamide Intermediate

Viso, Alma; Pradilla, Roberto Fernández de la; Ureña, Mercedes; Bates, Robert H.; Aguila, Miguel A. del; Colomer, Ignacio

doi:10.1021/jo202144k

Cited by 29 publications

(22 citation statements)

References 94 publications

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“…35 (t,1 H,J = 8.4 Hz,3.75 (t,1 H,J = 8.5 Hz,3 H,CH 2 ),5.48 (s,1 H,NH),5.74 (dd,1 H,J = 15.0,7.4 Hz), 6. 22-6.44 (m, 4 H (d,2 H,J = 8.2 Hz,, 7.78 (d,2 H,J = 8.3 Hz,. 13 = 16.8, 4.5, 2.9 Hz, H-5a), 3.…”

Section: Synthesis Of (-)-(2s3rr S )-2-butyl-1-n-(2-nitrobenzenesulmentioning

confidence: 99%

“…Data for 8d: R f 0.50 (30% EtOAc-hexane (d,2 H,J = 8.0 Hz,),7.50 (dd,2 H,J = 8.5,6.0 Hz), 7.76 (d,2 H,J = 8.5 Hz). 13 C NMR (75 MHz, CDCl 3 ) δ 21.…”

Section: Synthesis Of Alkynyl Sulfoxidesmentioning

confidence: 99%

“…= 10.8,8.8,6.5 Hz,, 5.87 (d,1 H,J = 1.7 Hz,6 H,, 7.77 (d,2 H,J = 8.3 Hz,. 13 (d,2 H,J = 8.3 Hz,. 13 (d,2 H,J = 8.1 Hz,, 7.41 (d,2 H,J = 8.1 Hz,.…”

Section: Synthesis Of (-)-(2z4zr S )-N-(tert-butoxycarbonyl)-4-(p-tunclassified

“…13 (d,2 H,J = 8.3 Hz,. 13 (d,2 H,J = 8.1 Hz,, 7.41 (d,2 H,J = 8.1 Hz,. 13 Method M: To a cold suspension (0 ºC) of sodium hydride (1.92 mg, 0.08 mmol, 1.3 equiv) in anhydrous THF (5.0 mL/mmol sulfoxide) was added a solution of the corresponding N-Boc dienyl sulfoxide (1.0 equiv) in anhydrous THF (5.0 mL/mmol sulfoxide), under an argon atmosphere and the mixture was stirred and warmed up to rt.…”

Section: Synthesis Of (-)-(2z4zr S )-N-(tert-butoxycarbonyl)-4-(p-tmentioning

confidence: 99%

“…1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 CDCl 3 ) δ 21.4 (CH 3 p-Tol), 21.5 (CH 3 p-Tol), 27.9 (CH 2 ), 29.2 (CH 2 ), 40.8 (C-6), 44.5 (CH 2 Cl), 49.4 (C- H, H-4), 1 H,5.92 (ddd,1 H,J = 10.2,3.9,2.2 Hz,7.29 (d,2 H,J = 8.0 Hz,pTol), 7.53 (d,2 H,J = 8.0 Hz,. 13 (d,1 H,J = 5.7 Hz),1 H),1 H). 13 C NMR (75 MHz, CDCl 3 ) δ 28.7, 40.7, 44.7, 46.2, 67.6, 80.3, 116.8, 125.5, 129.6, 129.9, 141.9.…”

Section: Synthesis Of (-)-(2s3rr S )-2-butyl-1-n-(2-nitrobenzenesulmentioning

confidence: 99%

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Synthesis of Enantiopure 3-Hydroxypiperidines from Sulfinyl Dienyl Amines by Diastereoselective Intramolecular Cyclization and [2,3]-Sigmatropic Rearrangement

et al. 2015

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The highly diastereoselective base-promoted intramolecular cyclization of a variety of enantiopure sulfinyl dienyl amines provides novel sulfinyl tetrahydropyridines that are readily converted to 3-hydroxy tetrahydropyridines via sigmatropic rearrangement. The influence of N- and C- substituents on the process has been studied. Procedures to shorten the sequence such as the tandem cyclization followed by [2,3]-sigmatropic rearrangement, as well as cyclization of the free amine, under Boc- or ArSO- deprotection conditions have been examined. Good to excellent levels of selectivity are generally observed for the reported transformations (dr: 75/25 to >98/2). A novel protocol to access substituted amino dienyl sulfoxides is also reported.

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Section: Synthesis Of (-)-(2s3rr S )-2-butyl-1-n-(2-nitrobenzenesulmentioning

confidence: 99%

“…Data for 8d: R f 0.50 (30% EtOAc-hexane (d,2 H,J = 8.0 Hz,),7.50 (dd,2 H,J = 8.5,6.0 Hz), 7.76 (d,2 H,J = 8.5 Hz). 13 C NMR (75 MHz, CDCl 3 ) δ 21.…”

Section: Synthesis Of Alkynyl Sulfoxidesmentioning

confidence: 99%

“…= 10.8,8.8,6.5 Hz,, 5.87 (d,1 H,J = 1.7 Hz,6 H,, 7.77 (d,2 H,J = 8.3 Hz,. 13 (d,2 H,J = 8.3 Hz,. 13 (d,2 H,J = 8.1 Hz,, 7.41 (d,2 H,J = 8.1 Hz,.…”

Section: Synthesis Of (-)-(2z4zr S )-N-(tert-butoxycarbonyl)-4-(p-tunclassified

Section: Synthesis Of (-)-(2z4zr S )-N-(tert-butoxycarbonyl)-4-(p-tmentioning

confidence: 99%

Section: Synthesis Of (-)-(2s3rr S )-2-butyl-1-n-(2-nitrobenzenesulmentioning

confidence: 99%

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Synthesis of Enantiopure 3-Hydroxypiperidines from Sulfinyl Dienyl Amines by Diastereoselective Intramolecular Cyclization and [2,3]-Sigmatropic Rearrangement

et al. 2015

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Addition of Non‐Stabilized Carbon‐Based Nucleophilic Reagents to Chiral N ‐Sulfinyl Imines

et al. 2019

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Natural products and pharmaceuticals that contain chiral branched amines are compounds of considerable interest. One strategy for preparing chiral branched amines involves the addition of a nucleophile to an imine bearing a readily cleavable chiral auxiliary. Sulfinamide‐based auxiliaries are well‐suited to this approach because (i) many sulfonamides are commercially available or can be prepared by efficient synthetic methods, (ii) N ‐sulfinyl aldimines and ketimines can be prepared in a straightforward manner, (iii) the chiral amine products are obtained with high diastereomeric ratios across a wide range of carbon‐based nucleophiles, and (iv) the N ‐sulfinyl group is cleaved under mild conditions. This chapter focuses on the addition of non‐stabilized, carbon‐based nucleophiles to N ‐sulfinyl aldimines and ketimines. Specifically, additions of alkyl, alkenyl, aryl, allylic, propargylic, alkynyl, and cyano nucleophiles are presented. Factors that can influence the stereoselectivity of the addition reaction are presented, along with the most prevalent reaction conditions employed for each class of nucleophile. Nucleophilic additions to N ‐sulfinyl aldimines and ketimines are key steps in the syntheses of a number of drug discovery targets and natural products, examples of which are highlighted in this review.

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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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An Approach to the Stereoselective Synthesis of Enantiopure Dihydropyrroles and Aziridines from a Common Sulfinyl-Sulfinamide Intermediate

Cited by 29 publications

References 94 publications

Synthesis of Enantiopure 3-Hydroxypiperidines from Sulfinyl Dienyl Amines by Diastereoselective Intramolecular Cyclization and [2,3]-Sigmatropic Rearrangement

Synthesis of Enantiopure 3-Hydroxypiperidines from Sulfinyl Dienyl Amines by Diastereoselective Intramolecular Cyclization and [2,3]-Sigmatropic Rearrangement

Addition of Non‐Stabilized Carbon‐Based Nucleophilic Reagents to Chiral N ‐Sulfinyl Imines

Sulfur‐Bearing Lithium Compounds in Modern Synthesis

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