Asymmetric Synthesis of (S)-(−)-Xylopinine. Use of the Sulfinyl Group as an Ipso Director in Aromatic SE

Mastranzo, Virginia M.; Yuste, Francisco; Ortíz, B.; Sánchez‐Obregón, Rubén; Toscano, Rubén A.; Ruano, José Luis Garcı́a

doi:10.1021/jo2007237

Cited by 38 publications

(21 citation statements)

References 27 publications

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“…Due to the successful results obtained in the literature using sulfoxides as chiral auxiliaries in directed lithiationdiastereoselective trapping sequences on aromatic compounds, [25][26][27][28][29][30][31][32][33][34] as well as in our precedent work, [35][36][37][38][39][40] and due to the robustness of the tert-butyl sulfinyl group, we chose the latter as the stereoinducer in our targeted transformation. † Dedicated to Professor Ei-ichi Negishi for his 80th birthday.…”

Section: Resultsmentioning

confidence: 99%

Atroposelective synthesis of axially chiral P,S-ligands based on arynes

et al. 2015

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The first atropo-selective aryl-aryl coupling based on arynes in the presence of a tert-butylsulfinyl group as the chiral auxiliary on the aryllithium nucleophile is described. The approach allows for the efficient access to a novel family of atropo-enantiopure biphenyl-based phosphine-thioether ligands. The new P,S heterodonor ligands were assessed in model palladium-catalyzed allylic substitution reactions.

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Section: Resultsmentioning

confidence: 99%

Atroposelective synthesis of axially chiral P,S-ligands based on arynes

et al. 2015

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“…Phenanthroindolizidines (50 [71,72]), phenanthroquinolizidines (51 [72]), tetrahydroprotoberberines (53 [67,68]), pyrroloisoquinolines (55 [69,70]), and diketopiperazine-fused THIQs (65 [73], vide infra) embody the tetrahydroisoquinoline skeleton, while indolizinoindoles (57 [74,75]), THBC-imidazolinediones (59 [76]), THBC-piperazinedione (61 [77,78]), the tetracyclic indole alkaloids (S)-harmicine (pyrrole-fused THBC, [66,79]), and (S)-eleagnine (1-methyl THBC, [66,80] represent the THBC-containing polyheterocycles. The additional ring can be already present in the imine substrate before the P-S reaction (type A) or can be built on the THIQ/THBC skeleton exploiting the functionality of some substituents (type B).…”

Section: Polyheterocyclesmentioning

confidence: 99%

The Pictet-Spengler Reaction Updates Its Habits

et al. 2020

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The Pictet-Spengler reaction (P-S) is one of the most direct, efficient, and variable synthetic method for the construction of privileged pharmacophores such as tetrahydro-isoquinolines (THIQs), tetrahydro-β-carbolines (THBCs), and polyheterocyclic frameworks. In the lustro (five-year period) following its centenary birthday, the P-S reaction did not exit the stage but it came up again on limelight with new features. This review focuses on the interesting results achieved in this period (2011–2015), analyzing the versatility of this reaction. Classic P-S was reported in the total synthesis of complex alkaloids, in combination with chiral catalysts as well as for the generation of libraries of compounds in medicinal chemistry. The P-S has been used also in tandem reactions, with the sequences including ring closing metathesis, isomerization, Michael addition, and Gold- or Brønsted acid-catalyzed N-acyliminium cyclization. Moreover, the combination of P-S reaction with Ugi multicomponent reaction has been exploited for the construction of highly complex polycyclic architectures in few steps and high yields. The P-S reaction has also been successfully employed in solid-phase synthesis, affording products with different structures, including peptidomimetics, synthetic heterocycles, and natural compounds. Finally, the enzymatic version of P-S has been reported for biosynthesis, biotransformations, and bioconjugations.

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“…The easy desulfinylation of the resulting compounds with Ra-Ni allowed the use of this methodology as one of the most efficient methods for preparing enantiomerically pure benzylic chiral centers. This methodology has been used for the synthesis of the optically pure (S)-(−)-xylopinine [161], where the ability of the sulfinyl group for acting as an ipso-director group in aromatic S E (Pictet-Spengler cyclization) is remarkable, allowing the creation of the isoquinoline skeleton during the removal of the sulfinyl group (Equation b, Scheme 8.46). Contrasting with the complete control of the stereoselectivity observed in these intramolecular processes, reactions of 2-p-tolylsulfinyl benzylcarbanions with aldehydes [157,160] afforded mixtures of two diastereoisomers, differing only in the configuration at the oxygenated carbon (Scheme 8.45).…”

Section: Lateral Lithiationmentioning

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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Asymmetric Synthesis of (S)-(−)-Xylopinine. Use of the Sulfinyl Group as an Ipso Director in Aromatic S_E

Cited by 38 publications

References 27 publications

Atroposelective synthesis of axially chiral P,S-ligands based on arynes

Atroposelective synthesis of axially chiral P,S-ligands based on arynes

The Pictet-Spengler Reaction Updates Its Habits

Sulfur‐Bearing Lithium Compounds in Modern Synthesis

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