Synthesis and [3,3]-sigmatropic rearrangements of 5-(pentafluorosulfanyl)-pent-3-en-2-ol, its homologues, and trifluoromethyl analogues

2021 ◽  
Author(s):  
Piotr Dudzinski ◽  
Wibke S. Husstedt ◽  
Andrej V. Matsnev ◽  
Joseph S. Thrasher ◽  
Guenter Haufe
Keyword(s):  
Allylic Alcohols ◽  
Sigmatropic Rearrangements

The synthesis of aliphatic (pentafluoro-λ6-sulfanyl)(SF5)-substituted compounds is more challenging than that of the related CF3-substituted analogues. Previous investigations of [3,3]-sigmatropic rearrangements of γ-SF5-substituted allylic alcohols failed to yield 3-SF5-substituted carboxylic...

[3,3]- Versus [1,3]-Sigmatropic Rearrangement of O-Substituted Allyl N-Acylmonothiocarbamates

1994 ◽  
Vol 59 (12) ◽  
pp. 2650-2662 ◽  
Author(s):  
Vlastimír Ficeri ◽  
Peter Kutschy ◽  
Milan Dzurilla ◽  
Ján Imrich
Keyword(s):  
Double Bond ◽  
Benzyl Alcohol ◽  
Sigmatropic Rearrangement ◽  
Allylic Alcohols ◽  
Cinnamyl Alcohol ◽  
Aromatic System ◽  
Sigmatropic Rearrangements ◽  
Sigmatropic Shift

Substituted allylic alcohols (2-buten-1-ol, 1-buten-3-ol, cinnamyl alcohol and 3-methyl-2-buten-1-ol) react with acyl isothiocyanates (4-chlorobenzoyl, 2,6-difluorobenzoyl, 3-phenylpropenoyl, 2-thienocarbonyl, 3-chloro-2-thienocarbonyl and 3-chloro-2-benzo[b]thienocarbonyl isothiocyanate) with the formation of highly reactive O-substituted allyl N-acylmonothiocarbamates, which either spontaneously or by heating in boiling benzene undergo [3,3]-sigmatropic rearrangement to S-substituted allyl N-acylmonothiocarbamates. The structure of S-esters with isomerized allylic group affords the unequivocal evidence of the [3,3]-sigmatropic route of studied rearrangement. Further heating of [3,3]-rearranged N-(4-chlorobenzoyl)monothiocarbamates results in the [1,3]-sigmatropic shift of monothiocarbamate group. Using arylalkyl alcohols with the allylic double bond inserted into an aromatic system the obtained O-esters either do not undergo any rearrangement (benzyl alcohol) or undergo [1,3]-sigmatropic rearrangement (2- and 3-furylmethanol and 1-(2-furyl)ethanol) to the corresponding S-esters. For explanation of this reaction the tandem of [3,3]- and [1,3]-sigmatropic rearrangements is suggested.

Active MnO2 As a Mild Oxidizing Reagent for the Controlled Oxidation of Benzylic and Allylic Alcohols

2012 ◽  
Vol 2 (6) ◽  
pp. 48-48
Author(s):  
Y. M. Nandurkar Y. M. Nandurkar ◽  
◽  
B. B. Bahule B. B. Bahule
Keyword(s):  
Allylic Alcohols

Bimetallic Radical Redox-Relay Catalysis for the Isomerization of Epoxides to Allylic Alcohols

2019 ◽  
Author(s):  
Ke-Yin Ye ◽  
Terry McCallum ◽  
Song Lin
Keyword(s):  
Ring Opening ◽  
High Reactivity ◽  
Hydrogen Atom Transfer ◽  
Organic Radicals ◽  
Epoxide Ring ◽  
Allylic Alcohols ◽  
Epoxide Ring Opening ◽  
Bond Forming ◽  
Co Catalysts ◽  
The Rich

Organic radicals are generally short-lived intermediates with exceptionally high reactivity. Strategically, achieving synthetically useful transformations mediated by organic radicals requires both efficient initiation and selective termination events. Here, we report a new catalytic strategy, namely bimetallic radical redox-relay, in the regio- and stereoselective rearrangement of epoxides to allylic alcohols. This approach exploits the rich redox chemistry of Ti and Co complexes and merges reductive epoxide ring opening (initiation) with hydrogen atom transfer (termination). Critically, upon effecting key bond-forming and -breaking events, Ti and Co catalysts undergo proton-transfer/electron-transfer with one another to achieve turnover, thus constituting a truly synergistic dual catalytic system.<br>

Direct and Selective Synthesis of Adipic and Other Dicarboxylic Acids by Palladium‐Catalyzed Carbonylation of Allylic Alcohols

2020 ◽  
Vol 59 (46) ◽  
pp. 20394-20398
Author(s):  
Ji Yang ◽  
Jiawang Liu ◽  
Yao Ge ◽  
Weiheng Huang ◽  
Helfried Neumann ◽  
...  
Keyword(s):  
Dicarboxylic Acids ◽  
Allylic Alcohols ◽  
Selective Synthesis ◽  
Palladium Catalyzed

scholarly journals Boron-catalyzed dehydrative allylation of 1,3-diketones and β-ketone esters with 1,3-diarylallyl alcohols in water

RSC Advances ◽  
2021 ◽  
Vol 11 (28) ◽  
pp. 17025-17031
Author(s):  
Guo-Min Zhang ◽  
Hua Zhang ◽  
Bei Wang ◽  
Ji-Yu Wang
Keyword(s):  
Allylic Alcohols

Allylic alcohols can directly dehydrated in water by B(C6F5)3, without any base additives.

Efficient synthesis of tetrahydrofurans with chiral tertiary allylic alcohols catalyzed by Ni/P-chiral ligand DI-BIDIME

2021 ◽  
Author(s):  
Yu Mu ◽  
Tao Zhang ◽  
Yaping Cheng ◽  
Wenzhen Fu ◽  
Zuting Wei ◽  
...  
Keyword(s):  
Reductive Cyclization ◽  
Allylic Alcohols ◽  
Chiral Ligand ◽  
Efficient Synthesis

Efficient nickel-catalyzed stereoselective asymmetric intramolecular reductive cyclization of O-alkynones with P-chiral bisphosphorus ligand DI-BIDIME is reported.

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