Zirconium and Titanium Mediated Hydroboration of Alkenes and Alkynes

doi:10.6023/cjoc202212022

Abstract

The transition metal-catalyzed hydroboration of alkenes and alkynes is one of the most efficient way for the production of boronate esters. This type of reaction is 100% atom economic, the starting material is readily available, and the products are diverse. It is noticed that most of the known catalytic systems are based on late-transition-metals such as Rh, Ir, Pd, Pt, Co, Fe and Cu. The use of early-transition-metals of zirconium and titanium, on the other hand, is very scarce. In this short review, the development of application in zirconium and titanium mediated hydroboration of alkene and alkyne is summarized, and the research trends of this area are also discussed.

Key words: zirconium, titanium, alkenes, alkynes, hydroboration

Cite this article

Sida Li, Xing-Zhong Shu, Lipeng Wu. Zirconium and Titanium Mediated Hydroboration of Alkenes and Alkynes[J]. Chinese Journal of Organic Chemistry, 2023, 43(5): 1751-1760.

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Fig. & Tab. 20

Scheme 1. Transformation and application of organoborons and hydroboration of alkenes and alkynes

Scheme 2. Synthesis of alkenyl (alkyl) boron mediated by stoichiometric zirconium

Scheme 3. Cp2ZrHCl-catalyzed hydroboration of alkynes and possible mechanism

Scheme 4. Cp2ZrHCl-catalyzed hydroboration of terminal alkynes and possible mechanism

Scheme 5. Hydroamination of terminal alkynes via Zr/Cu relay catalysis

Scheme 6. One-pot synthesis of cyclopropylboronic esters from terminal alkynes

Scheme 7. Zirconium-catalyzed synthesis of alkenylaminoboranes

Scheme 8. Cp2ZrHCl-catalyzed hydroboration of alkenes

Scheme 9. Dehydrogenative boration of alkenes enabled by zir- conium catalyst

Scheme 10. Zirconium-catalyzed synthesis of 1,1-diborylalkanes from alkenes

Scheme 11. Titanium-catalyzed alkenes hydroboration

Scheme 12. Titanium-catalyzed hydroboration of alkenes and possible mechanism

Scheme 13. Possible mechanism for titanium-catalyzed decaborane-olefin hydroborations

Scheme 14. Titanium-catalyzed cycloboration of olefins

Scheme 15. Titanium-mediated dehydrogenative borylation of ethylene

Scheme 16. Titanium-catalyzed dehydrogenative borylation of ethylene

Scheme 17. Titanium-catalyzed borylation of α-olefins with bis(diisopropylamino)chlorborane and possible mechanism

Scheme 18. Titanium-catalyzed hydroboration of alkynes

Scheme 19. Possible mechanism for titanium-catalyzed hydroboration of alkynes

Scheme 20. Novel titanium-catalyzed hydroboration of terminal alkynes and possible mechanism

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