Asymmetric Synthesis of Quaternary β‐Perfluorophenyl‐β‐amino‐indolin‐2‐ones

Zhang, Wenzhong; Sha, Wanxing; Zhu, Yi; Han, Jianlin; Soloshonok, Vadim A.; Pan, Yi

doi:10.1002/ejoc.201601645

Cited by 20 publications

(3 citation statements)

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“…In 2017, the Han group designed and synthesized a N - tert -butylsulfinyl-(perfluoro)benzaldimine 256 and used this imine as an electrophile in the asymmetric detrifluoroacetylative Mannich reactions (Scheme ). Pentafluorophenyl (perfluorophenyl) is an electronic antipode of the common phenyl group, − which also has been widely used in the chemical and biological area. The Mannich addition reactions of in situ generated enolates proceeded smoothly to give the corresponding quaternary β-perfluorophenyl-amino-indolin-2-ones 257 with moderate yields and diastereoselectivities.…”

Section: Modern Methods For Construction Of Quaternary C–f Stereogeni...mentioning

confidence: 99%

Modern Approaches for Asymmetric Construction of Carbon–Fluorine Quaternary Stereogenic Centers: Synthetic Challenges and Pharmaceutical Needs

et al. 2018

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New methods for preparation of tailor-made fluorine-containing compounds are in extremely high demand in nearly every sector of chemical industry. The asymmetric construction of quaternary C−F stereogenic centers is the most synthetically challenging and, consequently, the least developed area of research. As a reflection of this apparent methodological deficit, pharmaceutical drugs featuring C−F stereogenic centers constitute less than 1% of all fluorine-containing medicines currently on the market or in clinical development. Here we provide a comprehensive review of current research activity in this area, including such general directions as asymmetric electrophilic fluorination via organocatalytic and transition-metal catalyzed reactions, asymmetric elaboration of fluorine-containing substrates via alkylations, Mannich, Michael, and aldol additions, cross-coupling reactions, and biocatalytic approaches. CONTENTS

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Section: Modern Methods For Construction Of Quaternary C–f Stereogeni...mentioning

confidence: 99%

Modern Approaches for Asymmetric Construction of Carbon–Fluorine Quaternary Stereogenic Centers: Synthetic Challenges and Pharmaceutical Needs

et al. 2018

Self Cite

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“…Heterocyclic compounds can be obtained through strategies using Mannich reactions [164][165][166]. It was previously commented that the addition of ethyl 4-nitrobutanoante (203) to chiral sulfinyl imines under basic solvent-free conditions proceeded with high facial diastereoselectivity (Scheme 64 [143]).…”

Section: Stereocontrol Synthesis Through Mannich Nitro-mannich and Mukaiyama-mannich Reactions Of N-sulfinyl Iminesmentioning

confidence: 99%

N-tert-Butanesulfinyl imines in the asymmetric synthesis of nitrogen-containing heterocycles

Mendes¹,

Costa²,

Yus³

et al. 2021

Beilstein J. Org. Chem.

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The synthesis of nitrogen-containing heterocycles, including natural alkaloids and other compounds presenting different types of biological activities have proved to be successful employing chiral sulfinyl imines derived from tert-butanesulfinamide. These imines are versatile chiral auxiliaries and have been extensively used as eletrophiles in a wide range of reactions. The electron-withdrawing sulfinyl group facilitates the nucleophilic addition of organometallic compounds to the iminic carbon with high diastereoisomeric excess and the free amines obtained after an easy removal of the tert-butanesulfinyl group can be transformed into enantioenriched nitrogen-containing heterocycles. The goal of this review is to the highlight enantioselective syntheses of heterocycles involving the use of chiral N-tert-butanesulfinyl imines as reaction intermediates, including the synthesis of several natural products. The synthesis of nitrogen-containing heterocycles in which the nitrogen atom is not provided by the chiral imine will not be considered in this review. The sections are organized according to the size of the heterocycles. The present work will comprehensively cover the most pertinent contributions to this research area from 2012 to 2020. We regret in advance that some contributions are excluded in order to maintain a concise format.

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“…Alternatively, a transition state involving a sulfinimine in the s-trans conformation could be considered as well (not shown). 22,23 In contrast, Nsulfinylimine reduction with NaBH 4 is proposed to proceed via a chelated transition state. 17 With the Z-imine 5a, this would give TS-3, featuring Re-face attack, which was not observed.…”

Section: (R S R)-10 (R S S)-10mentioning

confidence: 99%

1,1,1-Trifluoropropan-2-ammonium triflate enantiomers: stereoselective synthesis and direct use in reaction with epoxides

Packer

Malassis

Wells

et al. 2017

Tetrahedron: Asymmetry

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A three-step synthesis of enantiomerically enriched 1,1,1-trifluoro-2-propanamine based on the use of a chiral sulfinamide auxiliary is described. Reduction of the geometrically pure Z-sulfinimine (NOE, HOE) with NaBH4 or L-selectride leads to the corresponding (R)-or (S)-configured amine derivatives (X-ray crystallographic analysis) in 92-96% de. The typical models to explain stereoselection for these reducing agents fail to rationalize the obtained stereoselectivities, and in situ imine isomerization is proposed to occur. The direct use of the hydrochloric acid salt (with excess Et3N) of this poorly nucleophilic amine for epoxide opening reactions is not possible due to faster reaction of chloride. Hence, a novel triflate salt is introduced, synthesized through facile sulfinamide hydrolysis with trimethylsilyl triflate, which can be used directly, without the need of isolating the pure amine beforehand.

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Asymmetric Synthesis of Quaternary β‐Perfluorophenyl‐β‐amino‐indolin‐2‐ones

Cited by 20 publications

References 81 publications

Modern Approaches for Asymmetric Construction of Carbon–Fluorine Quaternary Stereogenic Centers: Synthetic Challenges and Pharmaceutical Needs

Modern Approaches for Asymmetric Construction of Carbon–Fluorine Quaternary Stereogenic Centers: Synthetic Challenges and Pharmaceutical Needs

N-tert-Butanesulfinyl imines in the asymmetric synthesis of nitrogen-containing heterocycles

1,1,1-Trifluoropropan-2-ammonium triflate enantiomers: stereoselective synthesis and direct use in reaction with epoxides

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