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

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

Journal

European Journal of Organic Chemistry
ISSN: 1434-193X , E-ISSN: 1099-0690

Output data

Year: 2022, Volume: 2022, Number: 25, Article number : e202200547, Pages count : DOI: 10.1002/ejoc.202200547

Authors

Zaitseva Elvira R. ¹ , Smirnov Alexander Yu. ^1,2 , Timashev Vladimir I. ^3,4 , Malyshev Vadim I. ³ , Zhigileva Ekaterina A. ^1,4 , Mikhaylov Andrey A. ¹ , Medvedev Michael G. ³ , Baleeva Nadezhda S. ^1,2 , Baranov Mikhail S. ^1,2

Affiliations

1	Institute of Bioorganic Chemistry, Russian Academy of Sciences, Miklukho-Maklaya 16/10, 117997 Moscow, Russia
2	Pirogov Russian National Research Medical University, Ostrovitianov 1, 117997 Moscow, Russia
3	N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Science, Leninsky prosp. 47, 119991 Moscow, Russia
4	Lomonosov Moscow State University, Leninskie Gory 1 (3), 119991 Moscow, Russia

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.

Zaitseva E.R. , Smirnov A.Y. , Timashev V.I. , Malyshev V.I. , Zhigileva E.A. , Mikhaylov A.A. , Medvedev M.G. , Baleeva N.S. , Baranov M.S.
BF3 Mediated [1,5]‐Hydride Shift Triggered Cyclization: Thioethers Join the Game
European Journal of Organic Chemistry. 2022. V.2022. N25. e202200547 . DOI: 10.1002/ejoc.202200547 WOS Scopus OpenAlex

≡ Web of science:	WOS:000819991400001
≡ Scopus:	2-s2.0-85133586645
≡ OpenAlex:	W4280523808