Synthesis of Allylboronates via Zweifel‐type Deprotonative Olefination

Xu, Nuo; Xu, Jianeng; Zhu, Qing; Liu, Chao

doi:10.1002/adsc.202001351

Cited by 8 publications

(3 citation statements)

References 24 publications

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Section: New Elimination and Migration Patterns Involving The Zweifel...mentioning

confidence: 99%

“…This method features a different elimination strategy for the Zweifel-type olefination that can afford allylboronate products, which can be further transformed into many other valuable compounds (Scheme 8). 11 Besides 1,2-migration of alkenyl tetracoordinate boron complexes, other unsaturated systems, for example, their alkynyl analogues, could also undergo 1,2-migration under activation with appropriate electrophiles. However, in previously reported cases, only one phenyl group of the triphenyl-substituted tetracoordinate boron species could participate in migration, thus resulting in a low functionality utilization ratio of the tetracoordinate boron substrates.…”

Section: New Elimination and Migration Patterns Involving The Zweifel...mentioning

confidence: 99%

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Recent Progress on the Zweifel Olefination: An Update

Song,

2023

Synthesis

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During the past several decades, Zweifel olefination has emerged as one of the most powerful and reliable tools for constructing C–C double bonds. This reaction features high efficiency, good versatility, nonuse of transition metals, and perfect stereospecificity, which make it superior to many other olefination methods. Since the summary of Zweifel olefination’s 50-years history was published in 2017 by Aggarwal et al., remarkable achievements have been made in terms of employing new organometallic species, proceeding through electrochemical or photochemical pathways, and furnishing new kinds of products. This short review summarizes and discusses the very recent progress in Zweifel olefination and its latest application in natural products synthesis. 1 Introduction 2 Zweifel Olefination with New Organometallic Species 3 Zweifel Olefination with New Migrating Groups 4 Electrochemical and Photocatalyzed Zweifel Olefination 5 New Elimination and Migration Patterns of Zweifel Olefination 6 Zweifel Olefination in Natural Product Synthesis 7 Other Reactions Involving the Zweifel Olefination Mechanism 8 Conclusions and Outlook

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Section: New Elimination and Migration Patterns Involving The Zweifel...mentioning

confidence: 99%

Section: New Elimination and Migration Patterns Involving The Zweifel...mentioning

confidence: 99%

Recent Progress on the Zweifel Olefination: An Update

Song,

2023

Synthesis

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“…The corresponding products possessing a stereodefined trisubstituted vinylsilane could be further functionalized by decoration of the R group, increasing the structural complexity in a rapid and diverse manner. However, 1,1-disubstituted silyl allylborons have been barely studied and utilized in asymmetric synthesis because of their poor accessibility. First, it is difficult to enantioselectively construct the sterically demanding quaternary carbon bearing both bulky silyl and boryl groups.…”

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confidence: 99%

3-Silyl-3-Borylhex-4-Enoate: A Chiral Reagent for Asymmetric Crotylboration of Aldehydes

et al. 2022

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A nonracemic 3-silyl-3-borylhex-4-enoate reagent has been developed. Its asymmetric crotylboration of aldehydes provides Z-anti-homoallylic alcohols possessing a trisubstituted vinylsilane in high yields with excellent stereo- and enantioselectivity. Diverse decoration of vinylsilane and ester groups, as well as formation of functionalized THF rings, showcase the potential of the approach in the synthesis of polyketide natural products.

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Interception of Alkynyl Tetracoordinate Borons with Sulfur Electrophiles beyond the Zweifel Pathway

Ma,

An,

et al. 2024

Angewandte Chemie

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Zweifel reaction is a powerful strategy to construct olefins from alkenyl tetracoordinate borons in organoboron chemistry, however, it usually only involves one functional group migration and then undergoes an elimination process affording alkenes or alkynes exclusively. Herein, we disclose several intriguing interception of alkynyl tetracoordinate borons with sulfur electrophiles. Wherein, the substituted benzothiophenes are accessed by consecutive 1,2‐migrations and intramolecular electrophilic substitution, meanwhile, the challenging and elusive five/four‐membered boracycles are easily assembled, and an approach to alkenyl sulfides with good stereoselectivity was developed as well. Moreover, by adding readily available deuterium sources, the tetrasubstituted deuterated alkenyl sulfides with high deuteration rates are constructed. These protocols not only improve atom economy by prohibiting the elimination of Zweifel intermediate, but also enriches the reaction modes of alkynyl tetracoordinate borons achieving versatile value‐added sulfur‐containing molecules. Mechanistic investigations illustrate that dichlorosulfoxide (SOCl2) and dialkylaminosulfur trifluoride‐type reagents (DAST‐type) as surfur sources could promote dual 1,2‐aryl migration of alkynyl tetracoordinate borons, which are distinct from traditional Zweifel reaction, and the regulation of steric hindrance could also make four‐membered boracycles and alkenyl sulfides feasible. And these transformations feature novel reaction modes and unusual reaction mechanisms with valuable products in high efficiency.

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Synthesis of Allylboronates via Zweifel‐type Deprotonative Olefination

Cited by 8 publications

References 24 publications

Recent Progress on the Zweifel Olefination: An Update

Recent Progress on the Zweifel Olefination: An Update

3-Silyl-3-Borylhex-4-Enoate: A Chiral Reagent for Asymmetric Crotylboration of Aldehydes

Interception of Alkynyl Tetracoordinate Borons with Sulfur Electrophiles beyond the Zweifel Pathway

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