Iridium‐Catalyzed Asymmetric Hydrogenation of Benzo[<i>b</i>]thiophene 1,1‐Dioxides

Tosatti, Paolo; Pfaltz, Andreas

doi:10.1002/ange.201701409

Cited by 12 publications

(3 citation statements)

References 24 publications

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“…Recently, Pfaltz's group reported Ir−P,N complex catalyzed asymmetric hydrogenation of benzo[b]thiophene 1,1-dioxides, and the 2-and 3-aryl substituted substrates were hydrogenated with high conversions and excellent enantioselectivities (up to 99% ee). 14 However, poor conversions or moderate to good enantioselectivities were observed for the 2-alkyl-substituted substrates. The application of the catalyst/ligand investigated reported herein, Rh-(R,R)-f-spiroPhos, for the hydrogenation of 2-alkyl- substituted benzo[b]thiophene 1,1-dioxides yielded excellent enantioselectivities (up to 99% ee) for a wide range of 2-alkylsubstituted substrates 5 (Table 4).…”

Section: Asymmetric Hydrogenation Of Benzo[b]mentioning

confidence: 99%

“…However, only moderate to good enantioselectivities were achieved in the hydrogenation of the corresponding alkyl substituted substrates. 14 Zhang and co-workers developed Rh-catalyzed asymmetric hydrogenation of α-substituted vinyl sulfones and β-acetylamino acrylosulfones using DTBM-SegPhos and Tangphos, respectively, achieving high enantioselectivities for the (Z)-β-acetylamino acrylosulfones. 15,16 Thus, the substrate scope of the asymmetric hydrogenation of sulfones remains limited.…”

Section: Introductionmentioning

confidence: 99%

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Highly Efficient Enantioselective Synthesis of Chiral Sulfones by Rh-Catalyzed Asymmetric Hydrogenation

et al. 2019

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A highly efficient and enantioselective Rh-(R,R)-f-spiroPhos complex catalyzed hydrogenation of a series of unsaturated sulfones has been developed. With Rh-(R,R)-f-spiroPhos catalyst under mild conditions, not only the asymmetric hydrogenation of both the 3,3-diaryl and exocyclic α,β-unsaturated sulfones was first realized with up to 99.9% ee but also 3-alkyl-3-aryl and benzo[b]thiophene-1,1-dioxides were successfully hydrogenated to the corresponding chiral sulfones with excellent enantioselectivities (up to 99.4% ee) regardless of the steric hindrance, electronic property, and geometry of the substrates. Moreover, this reaction offers a route to (S)-(+)-ar-turmerone as a spice flavor, which is an important synthetic intermediate of pharmaceuticals.

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Section: Asymmetric Hydrogenation Of Benzo[b]mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Highly Efficient Enantioselective Synthesis of Chiral Sulfones by Rh-Catalyzed Asymmetric Hydrogenation

et al. 2019

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“…Regarding asymmetric and catalytic transformations, AH constitutes one of the most elegant strategies to afford chiral fragments with great atom economy [37] . In fact, several groups have synthetized and hydrogenated vinylic, allylic and homoallylic sulfones by using Ir [6a–c] or Rh complexes [6d–g] . However, they used tri‐ and tetra‐substituted olefins, which often encounter E / Z ‐selectivity issues in their preparation steps and may be hard to separate.…”

Section: Introductionmentioning

confidence: 99%

Three‐Component Palladium‐Catalyzed Tandem Suzuki‐Miyaura/Allylic Substitution: A Regioselective Synthesis of (2‐Arylallyl) Aryl Sulfones

Bellido,

Garçon,

Verdaguer

et al. 2024

Adv Synth Catal

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A one‐pot Pd‐catalyzed tandem process to prepare (2‐arylallyl) aryl sulfones has been developed. This strategy is based on the modular assembly of a boronic acid, a sodium sulfinate and 2‐bromoallyl acetate. The reaction is completely regioselective towards the terminal alkene, yielding (2‐arylallyl) aryl (or alkyl) sulfones with yields ranging from 56 to 93%. Control experiments together with DFT calculations allowed to propose a plausible reaction mechanism of the tandem reaction. The usefulness of this methodology has been demonstrated with the formal synthesis of the marketed drug Apremilast and of several natural products by asymmetric hydrogenation. Using the commercially available UbaPHOX iridium complex, chiral β‐methyl sulfones with up to 98% ee were obtained

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Solvent Controlled Transformation between Sulfonyl Hydrazides and Alkynes: Divergent Synthesis of Benzo[b]thiophene‐1,1‐dioxides and (E)‐β‐iodo Vinylsulfones

Wang

Zhang

et al. 2018

Adv Synth Catal

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A green, efficient and controllable transformation between sulfonyl hydrazides and alkynes leading to benzo[b]thiophene-1,1-dioxides and (E)b-iodo vinylsulfones via radical pathway has been developed. The reaction occurs rapidly in the presence of simply H 2 O 2 and KI without the help of any transition metal. The chemoselectivity of the reaction is determined by the solvent in which the process is performed: TFE favors the cyclic product, while H 2 O medium generates the iodosulfonylative product. Notably, this protocol also represents the first direct approach to the aggregationinduced-emmision (AIE) active benzo[b] thiophene-1,1-dioxides from readily available sulfonyl hydrazides and alkynes in one step.

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Iridium‐Catalyzed Asymmetric Hydrogenation of Benzo[b]thiophene 1,1‐Dioxides

Cited by 12 publications

References 24 publications

Highly Efficient Enantioselective Synthesis of Chiral Sulfones by Rh-Catalyzed Asymmetric Hydrogenation

Highly Efficient Enantioselective Synthesis of Chiral Sulfones by Rh-Catalyzed Asymmetric Hydrogenation

Three‐Component Palladium‐Catalyzed Tandem Suzuki‐Miyaura/Allylic Substitution: A Regioselective Synthesis of (2‐Arylallyl) Aryl Sulfones

Solvent Controlled Transformation between Sulfonyl Hydrazides and Alkynes: Divergent Synthesis of Benzo[b]thiophene‐1,1‐dioxides and (E)‐β‐iodo Vinylsulfones

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