Asymmetric catalytic construction of fully substituted carbon stereocenters using acyclic α-branched β-ketocarbonyls: the “Methyl Rule” widely exists

Sun, Deqian; Yang, Shuang; Fang, Xinqiang

doi:10.1039/d0qo00673d

Cited by 11 publications

(5 citation statements)

References 89 publications

(53 reference statements)

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“…Considering the promising performance of these P,N-ligands and the magic “methyl rule” of chiral ligand design, − we decided that novel ligands needed to be developed based on the skeleton of L14 . Simplified versions of this ligand were first used based on common linear ketones instead of a special camphor unit.…”

Section: Resultsmentioning

confidence: 99%

Catalytic Asymmetric Hydroalkoxylation and Formal Hydration and Hydroaminoxylation of Conjugated Dienes

et al. 2023

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The straightforward construction of stereogenic centers bearing unprotected functional groups, as in nature, has been a persistent pursuit in synthetic chemistry. Abundant applications of free enantioenriched allyl alcohol and allyl hydroxylamine motifs have made the asymmetric hydration and hydroaminoxylation of conjugated dienes from water and hydroxylamine, respectively, intriguing and efficient routes that have, however, been unachievable thus far. A fundamental challenge is the failure to realize transition-metal-catalyzed enantioselective C− O bond constructions via hydrofunctionalization of conjugated dienes. Here, we perform a comprehensive study toward the stereoselective formal hydration and hydroaminoxylation of conjugated dienes by synthesizing a set of new P,N-ligands and identifying an aryl-derived oxime as a surrogate for both water and hydroxylamine. Asymmetric hydroalkoxylation with new P,N-ligands is also elucidated. Furthermore, versatile derivatizations following hydration provide indirect but concise routes to formal hydrophenoxylation, hydrofluoroalkoxylation, and hydrocarboxylation of conjugated dienes that have been unreported thus far. Finally, a ligand-to-ligand hydrogen transfer process is proposed based on the results of preliminary mechanistic experiments.

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Section: Resultsmentioning

confidence: 99%

Catalytic Asymmetric Hydroalkoxylation and Formal Hydration and Hydroaminoxylation of Conjugated Dienes

et al. 2023

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“…The α ‐methyl β ‐keto amide 377 was converted to the α ‐sulfenylation product 380 in 99 % yield and 45 % ee (Scheme 76). [172] …”

Section: Reactivities Of β‐Keto Amidesmentioning

confidence: 99%

β‐Keto Amides: A Jack‐of‐All‐Trades Building Block in Organic Chemistry

Zheng

et al. 2021

Eur J Org Chem

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β‐Keto amides are a versatile class of compounds that find wide applications in organic chemistry owing to the juxtaposition of multiple reaction sites within their molecular structures. Due to the importance of β‐keto amides in modern organic chemistry, numerous novel preparation methods, synthetic applications and unprecedented reactivities have been recorded over the past decade. Taking advantage of transition‐metal‐catalysis and organocatalysis, β‐keto amides have emerged into a jack‐of‐all‐trades building block for many stereoselective or tandemized multicomponent reactions. But so far, no reviews have been documented on these recent achievements with β‐keto amides. Our Review aims to provide a thorough summary regarding: (a) the synthesis of β‐keto amides, (b) the reactivities of β‐keto amides, (c) the synthetic applications of β‐keto amides in various important heterocyclic compounds, and (d) the coordination of β‐keto amides with main group elements and transition metals and the relevant applications.

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“…Their asymmetric catalytic transformations have been extensively developed. 3 However, the synthesis of geometry-defined acyclic enolates with two sterically and electronically similar β-substituents (such as methyl and ethyl) presents a challenge. Achieving enantiofacial selectivity in the nucleophilic transformations for these cases mainly relies on using chiral auxiliaries or stoichiometric chiral reagents.…”

Section: Introductionmentioning

confidence: 99%

Stereoselective formal alkenylation of β,β-disubstituted enesulfinamides for constructing 1,5- and 1,4-dicarbonyl derivatives bearing less-accessible acyclic α-quaternary stereocenters

Zhu,

2023

Org. Chem. Front.

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Asymmetric catalytic construction of fully substituted carbon stereocenters using acyclic α-branched β-ketocarbonyls: the “Methyl Rule” widely exists

Abstract: The catalytic asymmetric construction of tetrasubstituted carbon stereocenters constitutes one of the most challenging research topics in organic synthesis, which further play vital roles in diverse fields including medicinal and...

Cited by 11 publications

References 89 publications

Catalytic Asymmetric Hydroalkoxylation and Formal Hydration and Hydroaminoxylation of Conjugated Dienes

Catalytic Asymmetric Hydroalkoxylation and Formal Hydration and Hydroaminoxylation of Conjugated Dienes

β‐Keto Amides: A Jack‐of‐All‐Trades Building Block in Organic Chemistry

Stereoselective formal alkenylation of β,β-disubstituted enesulfinamides for constructing 1,5- and 1,4-dicarbonyl derivatives bearing less-accessible acyclic α-quaternary stereocenters

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