Construction of Quaternary Centers Bearing both Trifluoromethyl and Phosphorus Substituents Based on Base Catalyzed 1,6-Hydrophosphonylation of δ-CF3 Substituted p-Quinone Methides

Construction of trifluoromethylated quaternary stereocenters via p-quinone methides

Chemical Communications ◽

10.1039/c9cc08936e ◽

2020 ◽

Vol 56 (20) ◽

pp. 3031-3034 ◽

Cited By ~ 3

Author(s):

Kyu Terashima ◽

Tomoko Kawasaki-Takasuka ◽

Tomohiro Agou ◽

Toshio Kubota ◽

Takashi Yamazaki

Keyword(s):

Synthetic Method ◽

Quinone Methides ◽

Quaternary Centers ◽

Quaternary Stereocenters

Development of a new synthetic method for the construction of quaternary centers with a CF3 group was realized by way of 1,6-addition of various nucleophiles to highly reactive δ-trifluoromethylated p-quinone methides generated in situ.

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Synthesis of spiro[2.5]octa-4,7-dien-6-one with consecutive quaternary centers via 1,6-conjugate addition induced dearomatization of para-quinone methides

Chemical Communications ◽

10.1039/c5cc06287j ◽

2015 ◽

Vol 51 (87) ◽

pp. 15831-15834 ◽

Cited By ~ 78

Author(s):

Kuo Gai ◽

Xinxin Fang ◽

Xuanyi Li ◽

Jinyi Xu ◽

Xiaoming Wu ◽

...

Keyword(s):

Conjugate Addition ◽

Quinone Methides ◽

One Pot ◽

Quaternary Centers

Spiro[2.5]octa-4,7-dien-6-one with consecutive quaternary centers was synthesized in one pot without the use of metals.

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ChemInform Abstract: Synthesis of Spiro[2.5]octa-4,7-dien-6-one with Consecutive Quaternary Centers via 1,6-Conjugate Addition Induced Dearomatization of para-Quinone Methides.

ChemInform ◽

10.1002/chin.201609041 ◽

2016 ◽

Vol 47 (9) ◽

pp. no-no

Author(s):

Kuo Gai ◽

Xinxin Fang ◽

Xuanyi Li ◽

Jinyi Xu ◽

Xiaoming Wu ◽

...

Keyword(s):

Conjugate Addition ◽

Quinone Methides ◽

Quaternary Centers

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Synthesis of Diarylmethanes Bearing CF 3 ‐ and CN‐Substituted All‐carbon Quaternary Centers and Diarylmalononitriles through Cyanation of δ‐Disubstituted Para ‐Quinone Methides

European Journal of Organic Chemistry ◽

10.1002/ejoc.202100095 ◽

2021 ◽

Author(s):

Xiaoguang Pan ◽

Min Cao ◽

Song Li ◽

Hengshan Wang ◽

Xigong Liu ◽

...

Keyword(s):

Quinone Methides ◽

Quaternary Centers

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Metal-Free Photoinduced Hydroalkylation Cascade Enabled by an Electron-Donor-Acceptor Complex

10.26434/chemrxiv.11912073 ◽

2020 ◽

Author(s):

José Tiago Menezes Correia ◽

Gustavo Piva da Silva ◽

Camila Menezes Kisukuri ◽

Elias André ◽

Bruno Pires ◽

...

Keyword(s):

Electron Donor ◽

Functional Group ◽

Photoexcited Electron ◽

One Pot ◽

Quaternary Centers ◽

Metal Free ◽

Acceptor Complex ◽

Catalyst Free ◽

Donor Acceptor ◽

Radical Cascade

A metal- and catalyst-free photoinduced radical cascade hydroalkylation of 1,7-enynes has been disclosed. The process is triggered by a SET event involving a photoexcited electron-donor-aceptor complex between NHPI ester and Hantzsch ester, which decomposes to afford a tertiary radical that is readily trapped by the enyne. <a>The method provides an operationally simple, robust and step-economical approach to the construction of diversely functionalized dihydroquinolinones bearing quaternary-centers. A sequential one-pot hydroalkylation-isomerization approach is also allowed giving access to a family of quinolinones. A wide substrate scope and high functional group tolerance was observed in both approaches</a>.

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Diverse Cyclopentenes via Enantioselective Cu-Catalyzed Desymmetrization

10.26434/chemrxiv.6894833.v1 ◽

2018 ◽

Author(s):

Reece Jacques ◽

Robert D. C. Pullin ◽

Stephen P. Fletcher

Keyword(s):

Ring Systems ◽

Quaternary Centers ◽

Stereogenic Centers

<div> <div> <div> <p>A highly regio-, diastereo- and enantioselective Cu-catalyzed desymmetrization of diverse meso-bisphosphates with alkyl zirconium nucleophiles has been developed. The reaction allows access to a broad range of functionalized cyclopentenes with up to three contiguous stereogenic centers, including quaternary centers and spirocyclic ring systems.</p></div></div></div>

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Diverse Cyclopentenes via Enantioselective Cu-Catalyzed Desymmetrization

10.26434/chemrxiv.6894833 ◽

2018 ◽

Author(s):

Reece Jacques ◽

Robert D. C. Pullin ◽

Stephen P. Fletcher

Keyword(s):

Ring Systems ◽

Quaternary Centers ◽

Stereogenic Centers

<div> <div> <div> <p>A highly regio-, diastereo- and enantioselective Cu-catalyzed desymmetrization of diverse meso-bisphosphates with alkyl zirconium nucleophiles has been developed. The reaction allows access to a broad range of functionalized cyclopentenes with up to three contiguous stereogenic centers, including quaternary centers and spirocyclic ring systems.</p></div></div></div>

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Synthesis of Nitrile-Bearing Quaternary Centers via an Equilibrium-Driven Transnitrilation and Anion-Relay Strategy

10.26434/chemrxiv.7834940 ◽

2019 ◽

Author(s):

Sebastien Alazet ◽

Michael West ◽

Purvish Patel ◽

Sophie Rousseaux

Keyword(s):

Building Blocks ◽

One Pot ◽

Quaternary Centers ◽

Synthetic Intermediates

The efficient preparation of nitrile-containing building blocks is of interest due to their utility as synthetic intermediates and their prevalence in pharmaceuticals. As a result, significant efforts have been made to develop methods to access these motifs which rely on safer and non-toxic sources of CN. Herein, we report that 2-methyl-2-phenylpropanenitrile is an efficient, non-toxic, electrophilic CN source for the synthesis of nitrile-bearing quaternary centers via a thermodynamic transnitrilation and anion-relay strategy. This one-pot process leads to nitrile products resulting from the gem-difunctionalization of alkyl lithium reagents.<br>

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