Friedel–Crafts reaction of indoles with vicinal tricarbonyl compounds generated in situ from 1,3-dicarbonyl compounds and TEMPO: highly selective synthesis of tertiary alcohols

RSC Advances ◽  
2015 ◽  
Vol 5 (109) ◽  
pp. 89906-89910 ◽  
Author(s):  
Jianwei Yan ◽  
Tianjun Ni ◽  
Fulin Yan ◽  
Jixia Zhang ◽  
Fangfang Zhuang
Keyword(s):  
Bond Cleavage ◽  
Selective Synthesis ◽  
Dicarbonyl Compounds ◽  
Tertiary Alcohols

A novel Friedel–Crafts reaction of indoles with vicinal tricarbonyl compounds generated in situ has been developed, forming indolyl tertiary alcohols. The process involves disproportionation of TEMPO, α-oxyamination, N–O bond cleavage and, finally, addition of the indole.

Recent Developments in the Asymmetric Detrifluoroacetylative Reactions of in situ Generated Mono-Fluorinated Enolates

2020 ◽  
Vol 24 (18) ◽  
pp. 2181-2191
Author(s):  
Li Wang ◽  
Ziyi Li ◽  
Jiang Liu ◽  
Jianlin Han ◽  
Hiroki Moriwaki ◽  
...  
Keyword(s):  
Organic Chemistry ◽  
Bond Cleavage ◽  
Synthetic Methodology ◽  
Research Topics ◽  
Synthetic Organic Chemistry ◽  
Nucleophilic Reactions ◽  
F Center ◽  
Recent Developments

The development of an efficient and mild synthetic methodology for the construction of bioactive fluorine-containing molecules represents one of the hot research topics in general synthetic organic chemistry. In this review, some recent progresses achieved in the development of detrifluoroacetylatively generated mono-fluorinated enolates via CC bond cleavage and their asymmetric nucleophilic reactions for assembly of chiral quaternary C-F center containing compounds.

scholarly journals Stereoselective Tandem Iridium-Catalyzed Alkene Isomerization-Cope Rearrangement of ω-diene Epoxides: Efficient Access to Acyclic 1,6-Dicarbonyl Compounds

2021 ◽  
Author(s):  
Rahul Suresh ◽  
Itai Massad ◽  
Ilan Marek
Keyword(s):  
Bond Cleavage ◽  
Cope Rearrangement ◽  
Dicarbonyl Compounds ◽  
Alkene Isomerization ◽  
Efficient Access

The Cope rearrangement of 2,3-divinyloxiranes, a rare example of epoxide C-C bond cleavage, results in 4,5-dihydrooxepines which are amenable to hydrolysis, furnishing 1,6-dicarbonyl compounds containing two contiguous stereocenters at the 3- and 4- positions. We employ...

Selective photoredox decarboxylation of α-ketoacids to allylic ketones and 1,4-dicarbonyl compounds dependent on cobaloxime catalysis

2020 ◽  
Vol 56 (83) ◽  
pp. 12530-12533 ◽  
Author(s):  
Hong Zhang ◽  
Qian Xiao ◽  
Xu-Kuan Qi ◽  
Xue-Wang Gao ◽  
Qing-Xiao Tong ◽  
...  
Keyword(s):  
Selective Synthesis ◽  
Photoredox Catalysis ◽  
Dicarbonyl Compounds

The selective synthesis of allylic ketones and 1,4-dicarbonyl compounds by photoredox/cobaloxime co-catalysis and photoredox catalysis, respectively, is described herein.

Molybdenum-Mediated One-Pot Synthesis of Pyrazoles from Isoxazoles

Synthesis ◽  
2019 ◽  
Vol 51 (20) ◽  
pp. 3796-3804 ◽  
Author(s):  
Marine Rey ◽  
Stéphane Beaumont
Keyword(s):  
Bond Cleavage ◽  
Direct Synthesis ◽  
Molybdenum Complex ◽  
One Pot ◽  
One Pot Synthesis ◽  
Wide Range ◽  
Hydrolysis Of ◽  
Substituted Pyrazoles

A one-pot approach for the direct synthesis of substituted pyrazoles from isoxazoles is reported. The process involves isoxazole N–O bond cleavage mediated by a molybdenum complex, in situ hydrolysis of the resulting β-amino enone to the corresponding 1,3-diketone, followed by pyrazole formation in the presence of hydrazine or substituted hydrazine. Good to excellent yields and regioselectivities are obtained with nonsymmetric isoxazoles. By using readily available starting materials, a wide range of substituted pyrazoles may be synthesized by this method.

Selective Synthesis of exo-Spiro[2′,2′-difluorocyclopropane-3′,2′-tropanes]

Synthesis ◽  
2020 ◽  
Vol 52 (07) ◽  
pp. 1015-1024
Author(s):  
Andrii Gerasov ◽  
Grygoriy A. Dolgonos ◽  
Aleksandr Yu. Mandzhulo ◽  
Alexey Ryabitsky ◽  
Volodymyr Fetyukhin ◽  
...  
Keyword(s):  
Activation Barrier ◽  
Protecting Groups ◽  
Selective Synthesis ◽  
Double Bonds ◽  
Lower Activation ◽  
Conformationally Restrained

Conformationally restrained exo-isomers of N-Boc-protected spiro[2′,2′-difluorocyclopropane-3′,2′-tropanes] were synthesized in 62–83% yield via absolutely diastereoselective cycloaddition of CF2, generated in situ from Me3SiCF3/NaI in refluxing THF, to double bonds of 3-alkylidenetropanes. Standard removal of Boc protecting groups afforded corresponding exo-spiro[2′,2′-difluorocyclopropane-3′,2′-tropane] hydrochlorides in 82–94% yields. DFT and CCSD(T) calculations revealed that the observed exo-selectivity of difluorocarbene addition is likely to be caused by a lower activation barrier of the exo-difluorocyclopropanation compared to the endo-reaction.

Cleavage of carbon–carbon bonds by radical reactions

2019 ◽  
Vol 48 (9) ◽  
pp. 2615-2656 ◽  
Author(s):  
Paramasivam Sivaguru ◽  
Zikun Wang ◽  
Giuseppe Zanoni ◽  
Xihe Bi
Keyword(s):  
Bond Cleavage ◽  
Radical Reactions ◽  
Carbon Bond ◽  
Carbon Carbon Bond ◽  
Carbon Carbon Bonds ◽  
Carbon Bonds ◽  
Cleavage Reactions

This review provides insights into the in situ generated radicals triggered carbon–carbon bond cleavage reactions.

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