Cp2TiCl2-Catalyzed Interaction of Methylenecycloalkane with BF3·THF

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Abstract

The Cp2TiCl2-catalyzed interaction of methylenecycloalkanes with BF3·THF in tetrahydrofuran was carried out for the first time with the formation of target 1-fluoro-1-boraspirocarbocycles and also isomerization products of a starting monomer (1-methylcycloalk-1-enes). The structure of reaction products was elucidated using one- (1H, 13C Dept, 11B, 19F) and two-dimensional (COSY, HSQC, HMBC) NMR spectroscopy, mass spectrometry combined with quantum-chemical calculations of 13C NMR chemical shifts.

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About the authors

L. I. Tulyabaeva

Institute of Petrochemistry and Catalysis, Ufa Federal Research Center, Russian Academy of Sciences

Author for correspondence.
Email: khusainova_ink@mail.ru
ORCID iD: 0000-0002-3159-2868
Russian Federation, Ufa

R. R. Salakhutdinov

Institute of Petrochemistry and Catalysis, Ufa Federal Research Center, Russian Academy of Sciences

Email: khusainova_ink@mail.ru
ORCID iD: 0000-0003-3631-0708
Russian Federation, Ufa

A. R. Tulyabaev

Institute of Petrochemistry and Catalysis, Ufa Federal Research Center, Russian Academy of Sciences

Email: khusainova_ink@mail.ru
ORCID iD: 0000-0002-6566-4794
Russian Federation, Ufa

T. V. Tyumkina

Institute of Petrochemistry and Catalysis, Ufa Federal Research Center, Russian Academy of Sciences

Email: khusainova_ink@mail.ru
ORCID iD: 0000-0001-8127-9135
Russian Federation, Ufa

M. F. Abdullin

Ufa Institute of Chemistry, Ufa Federal Research Center, Russian Academy of Sciences

Email: khusainova_ink@mail.ru
ORCID iD: 0000-0002-9894-213X
Russian Federation, Ufa

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Supplementary files

Supplementary Files
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1. JATS XML
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2. Scheme 1. Cp2TiCl2-catalyzed synthesis of 1,2-disubstituted boriranes 1,2.

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3. Scheme 2. Interaction of α-olefins with BF3 THF under the action of Cp2TiCl2.

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4. Scheme 3. α,ω-Dienes in Cp2TiCl2-catalyzed synthesis of boriranes.

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5. Scheme 4. Proposed scheme for the formation of a titanium hydride complex.

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6. Scheme 5. Proposed scheme for the formation of spiroborocarbocycles by the reaction of methylenecycloalkanes with BHal3 under the action of Cp2TiCl2.

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7. Scheme 6. Oxidation of 1-fluoro-substituted boraspirane 7.

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8. Scheme 7. Cp2TiCl2-catalyzed interaction of methylenecyclododecane with BF3·THF.

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9. Scheme 8. Cp2TiCl2-catalyzed interaction of methylenecycloalkanes with BF3 THF

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10. Fig. 1. NMR spectra 11B (a) and 19F (b) of the reaction mixture after the interaction of methylenecyclododecane with BF3 THF in the presence of Cp2TiCl2/Mg (CDCl3, 298 K)

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11. Fig. 2. Mass spectrum of organoboron compound 8

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12. Fig. 3. NMR spectra 1H (a) and 13C (b) (together with 13C DEPTQ) of the reaction mixture after the interaction of methylenecyclododecane with BF3 THF in the presence of Cp2TiCl2/Mg (CDCl3, 298 K)

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13. Fig. 4. HSQC (a) and HMBC (fragment) (b) experiments of the reaction mixture after the interaction of methylenecyclododecane with BF3 THF in the presence of Cp2TiCl2/Mg

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14. Fig. 5. Mass spectrum of 1-methylcyclododec-1-ene 9

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15. Fig. 6. Structure of (Z/E)-isomers of 1-methylcyclododec-1-ene optimized by the B3LYP/cc-pVDZ method (13C NMR chemical shifts are given in ppm)

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