TY - JOUR

T1 - TfOH-promoted reactions of TMS-ethers of CF3−pentenynoles with arenes. Synthesis of CF3-substituted pentenynes, indenes, and other carbocyclic structures

AU - Vasilyev, Aleksander V.

AU - Zerov, Aleksey V.

AU - Boyarskaya, Irina A.

AU - Khoroshilova, Olesya V.

AU - Lavrentieva, Irina N.

AU - Slita, Alexander V.

AU - Sinegubova, Ekaterina O.

AU - Zarubaev, Vladimir V.

N1 - Funding Information: This work was supported by Russian Scientific Foundation (Grant No. 18-13-00008). Spectral studies were performed at Center for Magnetic Resonance, Center for Chemical Analysis and Materials Research, and Research Center for X-ray Diffraction Studies of Saint Petersburg State University, Saint Petersburg, Russia. Publisher Copyright: © XXXX American Chemical Society Copyright: Copyright 2021 Elsevier B.V., All rights reserved.

PY - 2021/1/15

Y1 - 2021/1/15

N2 - Trimethylsilyl ethers of 1,5-diaryl-3-(trifluoromethyl)-pent-1-en-4-yn-3-oles [Ar−C≡C−C(CF3)(OSiMe3)−CH=CH−Ar′] in the superacid TfOH give rise to reactive conjugated CF3-allylic-propargylic cations [Ar−C≡C−C+(CF3)−CH=CH−Ar′]. These species react with arenes in the presence of 1.5 equiv of TfOH forming regio- and stereoselectively E-1,1,5-triaryl-3-(trifluoromethyl)-pent-2-en-4-ynes [Ar−C≡C−C(CF3)=CH−CHAr′(Ar″)] in good yields. In the excess of TfOH, these CF3-pentenynes are further intramolecularly cyclized into CF3-bicyclic dihydroanthracene derivatives (“helicopter”like molecules). The CF3-pentenynes may also react with arenes, as external nucleophiles, leading to CF3-indenes. These two main reaction pathways depend on internal nucleophilicity of aryl substituents in CF3-pentenynes and external nucleophilicity of aromatic molecules. Plausible cationic reaction mechanisms have been discussed. CF3-bicyclic dihydroanthracene derivatives have been studied regarding their cytotoxicity and virus-inhibiting activity against influenza virus A/Puerto Rico/8/34 (H1N1) in MDCK cell line.

AB - Trimethylsilyl ethers of 1,5-diaryl-3-(trifluoromethyl)-pent-1-en-4-yn-3-oles [Ar−C≡C−C(CF3)(OSiMe3)−CH=CH−Ar′] in the superacid TfOH give rise to reactive conjugated CF3-allylic-propargylic cations [Ar−C≡C−C+(CF3)−CH=CH−Ar′]. These species react with arenes in the presence of 1.5 equiv of TfOH forming regio- and stereoselectively E-1,1,5-triaryl-3-(trifluoromethyl)-pent-2-en-4-ynes [Ar−C≡C−C(CF3)=CH−CHAr′(Ar″)] in good yields. In the excess of TfOH, these CF3-pentenynes are further intramolecularly cyclized into CF3-bicyclic dihydroanthracene derivatives (“helicopter”like molecules). The CF3-pentenynes may also react with arenes, as external nucleophiles, leading to CF3-indenes. These two main reaction pathways depend on internal nucleophilicity of aryl substituents in CF3-pentenynes and external nucleophilicity of aromatic molecules. Plausible cationic reaction mechanisms have been discussed. CF3-bicyclic dihydroanthracene derivatives have been studied regarding their cytotoxicity and virus-inhibiting activity against influenza virus A/Puerto Rico/8/34 (H1N1) in MDCK cell line.

KW - PROPARGYLIC ALCOHOLS

KW - NUCLEOPHILIC-SUBSTITUTION

KW - CF3-ALLYL ALCOHOLS

KW - AROMATIC-COMPOUNDS

KW - CARBONYL-COMPOUNDS

KW - ALLYLIC ALCOHOLS

KW - ACID

KW - TRIFLUOROMETHYLATION

KW - ALKYLATION

KW - EFFICIENT

UR - http://www.scopus.com/inward/record.url?scp=85099083089&partnerID=8YFLogxK

UR - https://www.mendeley.com/catalogue/053a83b6-a4ed-39e8-ac78-24fbc7aaf8b8/

U2 - 10.1021/acs.joc.0c02361

DO - 10.1021/acs.joc.0c02361

M3 - Article

AN - SCOPUS:85099083089

VL - 86

SP - 1489

EP - 1504

JO - Journal of Organic Chemistry

JF - Journal of Organic Chemistry

SN - 0022-3263

IS - 2

ER -