» Articles » PMID: 33871126

Titanocene-Catalyzed [2+2] Cycloaddition of Bisenones and Comparison with Photoredox Catalysis and Established Methods

Overview
Specialty Chemistry
Date 2021 Apr 19
PMID 33871126
Citations 5
Authors
Affiliations
Soon will be listed here.
Abstract

Cp Ti(TFA) is a broadly applicable catalyst for the [2+2] cycloaddition of bisenones by inner-sphere electron transfer. The attractiveness of this mechanism is shown by comparison with outer-sphere ET methods. DFT calculations show that the reaction proceeds through a unique unfavorable 5-exo (the rate-determining step) and a favorable 4-exo cyclization.

Citing Articles

generation and conversion of a half-zirconocene catalyst for the synthesis of -acylpyrazoles.

Wu J, Yang M, Leng D, Hu Q, Yao Y, Sun H RSC Adv. 2025; 15(3):1747-1753.

PMID: 39835217 PMC: 11744458. DOI: 10.1039/d4ra08083a.


Zirconium and hafnium catalyzed C-C single bond hydroboration.

Li S, Jiao H, Shu X, Wu L Nat Commun. 2024; 15(1):1846.

PMID: 38418499 PMC: 10902336. DOI: 10.1038/s41467-024-45697-y.


Formal Anti-Markovnikov Addition of Water to Olefins by Titanocene-Catalyzed Epoxide Hydrosilylation: From Stoichiometric to Sustainable Catalytic Reactions.

Hothker S, Gansauer A Glob Chall. 2023; 7(7):2200240.

PMID: 37483422 PMC: 10362118. DOI: 10.1002/gch2.202200240.


Titanium Radical Redox Catalysis: Recent Innovations in Catalysts, Reactions, and Modes of Activation.

Wu X, Chang Y, Lin S Chem. 2022; 8(7):1805-1821.

PMID: 36213842 PMC: 9543366. DOI: 10.1016/j.chempr.2022.06.005.


Titanocene(III)-Catalyzed Precision Deuteration of Epoxides.

Henriques D, Rojo-Wiechel E, Klare S, Mika R, Hothker S, Schacht J Angew Chem Int Ed Engl. 2021; 61(6):e202114198.

PMID: 34845824 PMC: 9305931. DOI: 10.1002/anie.202114198.


References
1.
Gansauer A, von Laufenberg D, Kube C, Dahmen T, Michelmann A, Behlendorf M . Mechanistic study of the titanocene(III)-catalyzed radical arylation of epoxides. Chemistry. 2014; 21(1):280-9. DOI: 10.1002/chem.201404404. View

2.
Wang L, Jang H, Roh Y, Lynch V, Schultz A, Wang X . Diastereoselective cycloreductions and cycloadditions catalyzed by Co(dpm)(2)-silane (dpm = 2,2,6,6-tetramethylheptane-3,5-dionate): mechanism and partitioning of hydrometallative versus anion radical pathways. J Am Chem Soc. 2002; 124(32):9448-53. DOI: 10.1021/ja020223k. View

3.
Gansauer A, Lauterbach T, Geich-Gimbel D . Polarity matching of radical trapping: high yielding 3-exo and 4-exo cyclizations. Chemistry. 2004; 10(20):4983-90. DOI: 10.1002/chem.200400685. View

4.
Du J, Yoon T . Crossed intermolecular [2+2] cycloadditions of acyclic enones via visible light photocatalysis. J Am Chem Soc. 2009; 131(41):14604-5. PMC: 2761970. DOI: 10.1021/ja903732v. View

5.
Weigend F, Ahlrichs R . Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy. Phys Chem Chem Phys. 2005; 7(18):3297-305. DOI: 10.1039/b508541a. View