Asymmetric Synthesis of Allylic Sulfonic Acids: Enantio‐ and Regioselective Iridium‐Catalyzed Allylations of Na<sub>2</sub>SO<sub>3</sub>

Liu, Wei; Zhao, Xiaoming; Zhang, Liang; Zhao, Mingzhu

doi:10.1002/chem.201405058

Cited by 19 publications

(8 citation statements)

References 66 publications

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“…In 2014, Zhao and co-workers discovered that sodium sulfite could be used in Ir-catalyzed allylic substitution reactions to directly form chiral allylic sulfonic acids 521 under mild conditions. 364 Water was indispensable for the reactivity of this reaction, and a mixture of THF/water was found to be the optimal solvent system. The reaction conditions were compatible with a broad range of allylic carbonates, leading to formation of the branched allylic sulfonic acids in good to excellent yields with good to high regio-and enantioselectiv- ities (Scheme 269).…”

Section: Sulfinates and Sulfitesmentioning

confidence: 87%

Section: Ir-catalyzed Asymmetric Allylic Substitutions With Sulfur Se...mentioning

confidence: 99%

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Iridium-Catalyzed Asymmetric Allylic Substitution Reactions

et al. 2018

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In this review, we summarize the origin and advancements of iridiumcatalyzed asymmetric allylic substitution reactions during the past two decades. Since the first report in 1997, Ir-catalyzed asymmetric allylic substitution reactions have attracted intense attention due to their exceptionally high regio-and enantioselectivities. Ircatalyzed asymmetric allylic substitution reactions have been significantly developed in recent years in many respects, including ligand development, mechanistic understanding, substrate scope, and application in the synthesis of complex functional molecules. In this review, an explicit outline of ligands, mechanism, scope of nucleophiles, and applications is presented.

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Section: Sulfinates and Sulfitesmentioning

confidence: 87%

Section: Ir-catalyzed Asymmetric Allylic Substitutions With Sulfur Se...mentioning

confidence: 99%

Iridium-Catalyzed Asymmetric Allylic Substitution Reactions

et al. 2018

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“…Zhao et al have applied sodium sulfite as an S -nucleophile in an Ir-catalyzed allylic sulfonation reaction. The subsequent oxidative degradation with ozone gave ( R )-2-phenyl-2-sulfoacetic acid, which has been used in the synthesis of cefsulodin, a semisynthetic antibiotic (Scheme c) …”

Section: Intermolecular Allylic Substitutions In Very Short Routes To...mentioning

confidence: 99%

“…The subsequent oxidative degradation with ozone gave (R)-2-phenyl-2-sulfoacetic acid, which has been used in the synthesis of cefsulodin, a semisynthetic antibiotic (Scheme 5c). 19 Nguyen et al have developed the first highly enantio-and regioselective fluorination utilizing the chiral diene ligand L7 (Scheme 5d). 20 Although slightly outside the scope of this Account with respect to the ligand, we want to illustrate this method by an application in the synthesis of a 15-fluoro-prostaglandin precursor.…”

Section: Intermolecular Allylic Substitutions Inmentioning

confidence: 99%

Applications of Iridium-Catalyzed Asymmetric Allylic Substitution Reactions in Target-Oriented Synthesis

Helmchen

2017

Acc. Chem. Res.

301

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Metal catalyzed allylic substitution is a cornerstone of organometallic and synthetic chemistry. Enantioselective versions have been developed with catalysts derived from transition metals, most notably molybdenum, nickel, ruthenium, rhodium, iridium, palladium, and copper. The palladium- and the iridium-catalyzed versions have turned out to be particularly versatile in organic synthesis because of the very broad scope of the nucleophile and great functional group compatibility. Assets of the iridium-catalyzed reaction are the formation of branched, chiral products from simple monosubstituted allylic substrates, high degrees of regio- and enantioselectivity, and use of modular, readily available chiral ligands. The possibility to use carbon, nitrogen, oxygen, and sulfur compounds as well as fluoride as nucleophiles allows a wide range of chiral building blocks to be prepared. Our Account begins with the presentation of fundamental reaction schemes and chiral ligands. We will focus our discussion on reactions promoted by phosphoramidite ligands, though numerous chiral ligands have been employed. The subsequent section presents a brief overview of reaction mechanism and experimental conditions. Two versions of the iridium-catalyzed allylic substitution have emerged. In type 1 reactions (introduced in 1997), linear allylic esters are commonly used as substrates under basic reaction conditions. In type 2 reactions (introduced in 2007), environmentally friendly branched allylic alcohols can be reacted under acidic conditions; occasionally, derivatives of allylic alcohols have also been applied. A unique feature of the type 2 reactions is that highly electrophilic allylic intermediates can be brought to reaction with weakly activated alkenes. The subsequent text is ordered according to the strategies followed to transform allylic substitution products to desired targets, most of which are natural products or drugs. Syntheses starting with an intermolecular allylic substitution are discussed first. Some fairly complex targets, for example, the potent nitric oxide inhibitor (-)-nyasol and the drug (-)-protrifenbute, have been synthesized via less than five steps from simple starting materials. Most targets discussed are cyclic compounds. Intermolecular allylic substitution with subsequent ring closing metathesis is a powerful strategy for their synthesis. Highlights are stereodivergent syntheses of Δ-tetrahydrocannabinols (THC), wherein iridium- and organocatalysis are combined (dual catalysis). The combination of allylic alkylation with a Diels-Alder reaction was utilized to synthesize the ketide apiosporic acid and the drug fesoterodine (Toviaz). Sequential allylic amination, hydroboration and Suzuki-Miyaura coupling generates enones suitable for conjugate addition reactions; this strategy was employed in syntheses of a variety of alkaloids, for example, the poison frog alkaloid (+)-cis-195A (pumiliotoxin C). Intramolecular substitutions offer interesting possibilities to build up stereochemical complexity via short sy...

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“…The catalysts of iridium and chiral monophosphoramidite ligands were effective in asymmetric allylic aminations, , etherifications, and sulfonations of achiral allylic esters and alcohols. The results were summarized in Table .…”

Section: Allylic Substitutionmentioning

confidence: 99%

Chiral Monophosphorus Ligands for Asymmetric Catalytic Reactions

Tang

2016

ACS Catal.

226

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Chiral monophosphorus ligands are playing an important role for the recent advances in asymmetric catalysis. This review summarizes the latest progress in various asymmetric catalytic reactions with the employment of chiral monophosphorus ligands including asymmetric allylic substitution, asymmetric dearomative arylation, asymmetric Heck reaction, asymmetric cross-coupling, asymmetric C–H bond functionalization, asymmetric coupling of π systems, asymmetric addition, asymmetric hydrogenation, and asymmetric organocatalytic reactions. The new reactivity, selectivity, and reaction mechanism enabled by these chiral monophosphorus ligands are discussed.

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Asymmetric Synthesis of Allylic Sulfonic Acids: Enantio‐ and Regioselective Iridium‐Catalyzed Allylations of Na₂SO₃

Cited by 19 publications

References 66 publications

Iridium-Catalyzed Asymmetric Allylic Substitution Reactions

Iridium-Catalyzed Asymmetric Allylic Substitution Reactions

Applications of Iridium-Catalyzed Asymmetric Allylic Substitution Reactions in Target-Oriented Synthesis

Chiral Monophosphorus Ligands for Asymmetric Catalytic Reactions

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Asymmetric Synthesis of Allylic Sulfonic Acids: Enantio‐ and Regioselective Iridium‐Catalyzed Allylations of Na2SO3

Cited by 19 publications

References 66 publications

Iridium-Catalyzed Asymmetric Allylic Substitution Reactions

Iridium-Catalyzed Asymmetric Allylic Substitution Reactions

Applications of Iridium-Catalyzed Asymmetric Allylic Substitution Reactions in Target-Oriented Synthesis

Chiral Monophosphorus Ligands for Asymmetric Catalytic Reactions

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Asymmetric Synthesis of Allylic Sulfonic Acids: Enantio‐ and Regioselective Iridium‐Catalyzed Allylations of Na₂SO₃