BF3 Mediated [1,5]-Hydride Shift Triggered Cyclization: Thioethers Join the Game

Elvira R. Zaitseva; Alexander Yu Smirnov; Vladimir I. Timashev; Vadim I. Malyshev; Ekaterina A. Zhigileva; Andrey A. Mikhaylov; Michael G. Medvedev; Nadezhda S. Baleeva; Mikhail S. Baranov

doi:10.1002/ejoc.202200547

BF₃ Mediated [1,5]-Hydride Shift Triggered Cyclization: Thioethers Join the Game

Elvira R. Zaitseva, Alexander Yu Smirnov, Vladimir I. Timashev, Vadim I. Malyshev, Ekaterina A. Zhigileva, Andrey A. Mikhaylov, Michael G. Medvedev, Nadezhda S. Baleeva, Mikhail S. Baranov^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

7 Citations (Scopus)

Abstract

2-(2-(Benzylthio)benzylidene)malonates can undergo the 1,5-hydride shift triggered cyclization resulting in thiachromanes in 45–84 % yield. Boron trifluoride as a reaction promotor is the key to success. DFT calculations revealed that the reaction proceeds via a chelate BF2 complex, which was confirmed by NMR-analysis. Experimental and theoretical comparison of nitrogen, sulfur and carbon analogues revealed that sulfur derivatives have the highest activation barrier for the hydride transfer due to the unfavorable transition state geometry, which explains the lack of previous reports on 1,5-hydride shifts in (alkylthio)styrenes.

Original language	English
Article number	e202200547
Number of pages	6
Journal	European Journal of Organic Chemistry
Volume	2022
Issue number	25
DOIs	https://doi.org/10.1002/ejoc.202200547
Publication status	Published - 7 Jul 2022
Externally published	Yes

Funding

The authors gratefully acknowledge support from the Russian Science Foundation, grant No. 20‐73‐10195. This work has been carried out using computing resources of the federal collective usage center Complex for Simulation and Data Processing for Mega‐science Facilities at NRC “Kurchatov Institute”, http://ckp.nrcki.ru/. The research is carried out using the equipment of the shared research facilities of HPC computing resources at Lomonosov Moscow State University.[31] The Siberian Branch of the Russian Academy of Sciences (SB RAS) Siberian Supercomputer Center is gratefully acknowledged for providing supercomputer facilities. The authors gratefully acknowledge support from the Russian Science Foundation, grant No. 20-73-10195. This work has been carried out using computing resources of the federal collective usage center Complex for Simulation and Data Processing for Mega-science Facilities at NRC “Kurchatov Institute”, http://ckp.nrcki.ru/. The research is carried out using the equipment of the shared research facilities of HPC computing resources at Lomonosov Moscow State University.[31] The Siberian Branch of the Russian Academy of Sciences (SB RAS) Siberian Supercomputer Center is gratefully acknowledged for providing supercomputer facilities.

All Science Journal Classification (ASJC) codes

Physical and Theoretical Chemistry
Organic Chemistry

Access to Document

10.1002/ejoc.202200547

Cite this

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title = "BF3 Mediated [1,5]-Hydride Shift Triggered Cyclization: Thioethers Join the Game",

abstract = "2-(2-(Benzylthio)benzylidene)malonates can undergo the 1,5-hydride shift triggered cyclization resulting in thiachromanes in 45–84 % yield. Boron trifluoride as a reaction promotor is the key to success. DFT calculations revealed that the reaction proceeds via a chelate BF2 complex, which was confirmed by NMR-analysis. Experimental and theoretical comparison of nitrogen, sulfur and carbon analogues revealed that sulfur derivatives have the highest activation barrier for the hydride transfer due to the unfavorable transition state geometry, which explains the lack of previous reports on 1,5-hydride shifts in (alkylthio)styrenes.",

author = "Zaitseva, {Elvira R.} and Smirnov, {Alexander Yu} and Timashev, {Vladimir I.} and Malyshev, {Vadim I.} and Zhigileva, {Ekaterina A.} and Mikhaylov, {Andrey A.} and Medvedev, {Michael G.} and Baleeva, {Nadezhda S.} and Baranov, {Mikhail S.}",

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AU - Zaitseva, Elvira R.

AU - Smirnov, Alexander Yu

AU - Timashev, Vladimir I.

AU - Malyshev, Vadim I.

AU - Zhigileva, Ekaterina A.

AU - Mikhaylov, Andrey A.

AU - Medvedev, Michael G.

AU - Baleeva, Nadezhda S.

AU - Baranov, Mikhail S.

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AB - 2-(2-(Benzylthio)benzylidene)malonates can undergo the 1,5-hydride shift triggered cyclization resulting in thiachromanes in 45–84 % yield. Boron trifluoride as a reaction promotor is the key to success. DFT calculations revealed that the reaction proceeds via a chelate BF2 complex, which was confirmed by NMR-analysis. Experimental and theoretical comparison of nitrogen, sulfur and carbon analogues revealed that sulfur derivatives have the highest activation barrier for the hydride transfer due to the unfavorable transition state geometry, which explains the lack of previous reports on 1,5-hydride shifts in (alkylthio)styrenes.

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