Allyl 4-Chlorophenyl Sulfone as a Versatile 1,1-Synthon for Sequential α-Alkylation/Cobalt-Catalyzed Allylic Substitution

Synthesis ◽  
2020 ◽  
Vol 52 (13) ◽  
pp. 1934-1946
Author(s):  
Masahiro Kojima ◽  
Shigeki Matsunaga ◽  
Tomoyuki Sekino ◽  
Shunta Sato ◽  
Kazuki Kuwabara ◽  
...  
Keyword(s):  
Side Chains ◽  
Allylic Substitution ◽  
Catalytic Method ◽  
Metal Catalyzed ◽  
High Yields ◽  
Unique Potential

Despite their unique potential as rare 1,1-dipole synthons, allyl sulfones are rarely used in target-oriented syntheses, likely due to the lack of a general catalytic method for their branch-selective allylic substitution. Herein, we identified allyl 4-chlorophenyl sulfone as a versatile linchpin for both base-mediated α-derivatization and subsequent cobalt-catalyzed allylic substitution. The sequential transformations allow for highly regioselective access to branched allylic substitution products with a variety of aliphatic side chains. The photoredox-enabled­ ­cobalt catalysis is indispensable for achieving high yields and regioselectivity­ for the desulfonylative substitution in contrast to traditional metal-catalyzed protocols, which lead to inferior outcomes in the corresponding transformations.

scholarly journals Palladium-catalyzed regio- and enantioselective migratory allylic C(sp3)-H functionalization

2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Ye-Wei Chen ◽  
Yang Liu ◽  
Han-Yu Lu ◽  
Guo-Qiang Lin ◽  
Zhi-Tao He
Keyword(s):  
Organic Synthesis ◽  
Allylic Substitution ◽  
Palladium Hydride ◽  
Substitution Process ◽  
Wide Range ◽  
Leaving Group ◽  
Palladium Catalyzed ◽  
Potential Factors ◽  
Metal Catalyzed ◽  
High Yields

AbstractTransition metal-catalyzed asymmetric allylic substitution with a suitably pre-stored leaving group in the substrate is widely used in organic synthesis. In contrast, the enantioselective allylic C(sp3)-H functionalization is more straightforward but far less explored. Here we report a catalytic protocol for the long-standing challenging enantioselective allylic C(sp3)-H functionalization. Through palladium hydride-catalyzed chain-walking and allylic substitution, allylic C-H functionalization of a wide range of acyclic nonconjugated dienes is achieved in high yields (up to 93% yield), high enantioselectivities (up to 98:2 er), and with 100% atom efficiency. Exploring the reactivity of substrates with varying pKa values uncovers a reasonable scope of nucleophiles and potential factors controlling the reaction. A set of efficient downstream transformations to enantiopure skeletons showcase the practical value of the methodology. Mechanistic experiments corroborate the PdH-catalyzed asymmetric migratory allylic substitution process.

Transition-Metal-Catalyzed Allylic Substitution and Titanocene-Catalyzed Epoxypolyene Cyclization as a Powerful Tool for the Preparation of Terpenoids.

ChemInform ◽  
2006 ◽  
Vol 37 (52) ◽  
Author(s):  
Andreas Gansaeuer ◽  
Jose Justicia ◽  
Antonio Rosales ◽  
Dennis Worgull ◽  
Bjoern Rinker ◽  
...  
Keyword(s):  
Transition Metal ◽  
Allylic Substitution ◽  
Transition Metal Catalyzed ◽  
Metal Catalyzed

The Synthesis of Novel Oligomer 4,8-Di(4-hexyl-2-thienyl)-2λ4δ2-Benzo[1,2-c;4,5-c’]bis[1,2,5]-Thiadiazole

2012 ◽  
Vol 602-604 ◽  
pp. 696-699
Author(s):  
Xiao Xiao Zhuang ◽  
Xiao Long Lei ◽  
Xiao Xia Sun
Keyword(s):  
Side Chains ◽  
Coupling Reactions ◽  
Low Bandgap ◽  
Palladium Catalyzed ◽  
Efficient Route ◽  
High Yields ◽  
Bandgap Materials

Heterocyclic oligomer based on BBT bearing solubilizing side chains have been synthesized in high yields over six steps from readily available starting materials. This approach offers a much milder, shorter, and more efficient route to BBT derivatives than current methods. This unit can then be used in the synthesis of low bandgap materials via palladium-catalyzed coupling reactions.

Transition metal-catalyzed allylic substitution reactions with unactivated allylic substrates

2015 ◽  
Vol 44 (22) ◽  
pp. 7929-7967 ◽  
Author(s):  
Nicholas A. Butt ◽  
Wanbin Zhang
Keyword(s):  
Transition Metal ◽  
Allylic Substitution ◽  
Substitution Reactions ◽  
Recent Developments ◽  
Transition Metal Catalyzed ◽  
Metal Catalyzed

This review highlights recent developments in the area of transition metal-catalyzed allylic substitution reactions with unactivated allylic substrates.

Synthesis of [6,7]-Dihydro-[1,4]-Dioxino-[2,3-f][2,1,3]-Benzothiadiazole: A Novel Building Block for Electron-Poor Conjugated Polymers"

2011 ◽  
Vol 284-286 ◽  
pp. 601-606 ◽  
Author(s):  
Xiao Xia Sun ◽  
Xiao Xiao Zhuang ◽  
Ying Chun Li ◽  
Xi Mei Liu ◽  
Ya Zhou Lou
Keyword(s):  
Conjugated Polymers ◽  
Building Block ◽  
Coating Process ◽  
Side Chains ◽  
Good Solubility ◽  
Multistep Synthesis ◽  
High Yields

Heterocyclic monomers based on 2,1,3-benzothiadiazole bearing solubilizing side chains have been synthesized in high yields over four steps from readily available starting materials. A multistep synthesis of the electron-poor 6, 7-dihydro-1, 4-dioxino-[2, 3-f][2,1,3]-benzothiadiazole are presented. The new dificient acceptor has good solubility in organic aolvents to permit an appropriate coating process.

Microbial Formation of Substituted Styrenes

1989 ◽  
Vol 44 (9-10) ◽  
pp. 765-770 ◽  
Author(s):  
Hans-Adolf Arfmann ◽  
Wolf-Rainer Abraham
Keyword(s):  
Carboxylic Acids ◽  
Benzene Ring ◽  
Cinnamic Acid ◽  
Methoxy Group ◽  
Methyl Chloride ◽  
Side Chains ◽  
Cinnamic Acids ◽  
Cinnamic Acid Derivatives ◽  
Aromatic Carboxylic Acids ◽  
High Yields

Various mono- and disubstituted cinnamic acid derivatives and aromatic carboxylic acids with saturated side chains were incubated mainly with Bacillus, Candida, Hansenula, and Saccharomyces strains. The cinnamic acids carrying a hydroxy- and/or a methoxy group at the 3- and/or 4-position of the benzene ring were decarboxylated with high yields. Most of the reactions were terminated within 24 to 48 h. Substitution at other ring positions afforded also decarboxylation, but at much lower yields. Derivatives with other residues like methyl, chloride, or bromide were not transform ed to the respective styrene. None of the saturated aromatic carboxylic acids could be decarboxylated by the strains used.

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