Two Catalytic Methods of an Asymmetric Wittig [2,3]-Rearrangement

Ošeka, Maksim; Kimm, Mariliis; Järving, Ivar; Lippur, Kristin; Kanger, Tõnis

doi:10.1021/acs.joc.6b02786

Cited by 20 publications

(20 citation statements)

References 40 publications

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“…Secondly, nucleophilic attack on an alkyne may compete with direct [2,3] Wittig rearrangement. Based on Lewis acid catalyzed [2,3] Wittig rearrangements and our previous work, we envisioned that an N , N ′‐dioxide/Lewis acid complex could engage an anionic propargyloxyoxindole substrate by coordination and induce stereoselective rearrangement. Herein, we describe the use of chiral N , N ′‐dioxide/Ni II as catalysts leading to various 3‐hydroxy 3‐substituted oxindoles bearing allenyl groups in excellent yields with high ee values (up to 99 % yield and 99 % ee ).…”

Section: Methodsmentioning

confidence: 99%

Nickel(II)‐Catalyzed Asymmetric Propargyl [2,3] Wittig Rearrangement of Oxindole Derivatives: A Chiral Amplification Effect

Zhang

Dong

et al. 2018

Angewandte Chemie

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A highly enantioselective [2,3] Wittig rearrangement of oxindole derivatives was realized by using a chiral N,N′‐dioxide/NiII complex as the catalyst under mild reaction conditions. A strong chiral amplification effect was observed, and allowed access to chiral 3‐hydroxy 3‐substituted oxindoles bearing allenyl groups in high yields and enantioselectivities (up to 92 % ee) by using a ligand with only 15 % ee. A reasonable explanation was given based on the experimental investigations and X‐ray crystal structures of enantiomerically pure and racemic catalysts. Moreover, the first catalytic kinetic resolution of racemic oxindole derivatives by a [2,3] Wittig rearrangement was realized with high efficiency and stereoselectivity.

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Section: Methodsmentioning

confidence: 99%

Nickel(II)‐Catalyzed Asymmetric Propargyl [2,3] Wittig Rearrangement of Oxindole Derivatives: A Chiral Amplification Effect

Zhang

Dong

et al. 2018

Angewandte Chemie

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“…In 2016, Kanger and co‐workers developed a highly enantioselective Cinchona alkaloid derived squaramide Cat‐19 catalyzed [2,3]‐sigmatropic rearrangement of oxindole derivatives 78 . Various enantioenriched 3‐hydroxy 3‐substituted oxindoles 79 were synthesized in high enantiomeric purities and moderate diastereoselectivities (Scheme ).…”

Section: Enantioselective [23]‐sigmatropic Rearrangementmentioning

confidence: 99%

Recent Advances in Catalytic Enantioselective Rearrangement

Wang

Zhu

2019

Eur J Org Chem

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Among the fundamental chemical transformations in organic synthesis, rearrangement has been recognized as powerful and reliable reactions for the construction of carbon–carbon or carbon–heteroatom bonds. Benefiting from the advance of the novel catalytic system, catalyst design and activation mode, the chemistry of enantioselective rearrangements has experienced ever‐growing development recently and has been successfully used in the synthesis of chiral non‐racemic building blocks, natural products, and other valuable compounds. We present herein a survey of the recent development on the catalytic enantioselective rearrangement (from 2013 onward) organized according to the rearrangement type.

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“…[10] Our group previously reported an asymmetric [2,3]-Wittig rearrangement of oxindole, malonate and cyclopentanone derivatives, in addition to an example of a diastereoselective [2,3]-sigmatropic rearrangement of N-allyl ammonium ylides. [11][12][13][14] In 2006, Gaunt et al described the first asymmetric organocatalytic rearrangement on aliphatic cinnamyloxyketones. [15] Almost a decade later, Denmark obtained moderate results using phase-transfer catalysis on allyloxy oxindole derivatives (ee up to 54 %).…”

Section: Introductionmentioning

confidence: 99%

Asymmetric Organocatalytic [2,3]‐Wittig Rearrangement of Cyclohexanone Derivatives

et al. 2021

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Asymmetric rearrangement reactions are one of the perfect tools for the construction of new carbon-carbon bonds in an enantioselective manner. The enantioselective [2,3]-Wittig rearrangement of cinnamyloxycyclohexanone derivatives, catalyzed by a commercially available primary amine, provided α-hydroxy ketones with high diastereo-and enantioselectivity. A new and straightforward procedure for the synthesis of cinnamyloxycyclohexanone derivatives was developed.

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Two Catalytic Methods of an Asymmetric Wittig [2,3]-Rearrangement

Abstract: Two different approaches for asymmetric catalytic Wittig [2,3]-rearrangement were developed. Allyloxymalonate derivatives were converted into homoallyl alcohols via organocatalytic or Ca-catalyzed pathways in moderate to high enantioselectivities.

Cited by 20 publications

References 40 publications

Nickel(II)‐Catalyzed Asymmetric Propargyl [2,3] Wittig Rearrangement of Oxindole Derivatives: A Chiral Amplification Effect

Nickel(II)‐Catalyzed Asymmetric Propargyl [2,3] Wittig Rearrangement of Oxindole Derivatives: A Chiral Amplification Effect

Recent Advances in Catalytic Enantioselective Rearrangement

Asymmetric Organocatalytic [2,3]‐Wittig Rearrangement of Cyclohexanone Derivatives

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