Recent Advances in Hydrochlorination of Alkenes

doi:10.6023/cjoc202105057

Abstract

Organochlorides have been widely used in medicine, pesticides, materials and other fields. In addition, organochlorides are also important synthetic building blocks. They have participated in a variety of reactions, such as free radical reactions, substitution reactions and cross-coupling reactions. The hydrochlorination of olefins is one of the most direct and efficient methods for the synthesis of organochlorides, and remakable breakthroughs have been made in the past thirty years. The research progress of olefin hydrochlorination in the past three decades is introduced. According to whether metal catalysis is involved, it is mainly classified into two categories: metal-free alkene hydrochlorination and metal-catalyzed alkene hydrochlorination. Different type of hydrochlorination reactions and related mechanisms are summarized. In addition, the future development direction of alkene hydrochlorination is prospected.

Key words: alkene, hydrochlorination, hydrogen chloride, organochloride, metal catalysis

Cite this article

Yaoxin Wang, Chen Cui, Xiaohui Yang. Recent Advances in Hydrochlorination of Alkenes[J]. Chinese Journal of Organic Chemistry, 2021, 41(10): 3808-3815.

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Fig. & Tab. 21

Scheme 1. General methodologies for hydrochlorination of alkenes

Scheme 2. Silica gel mediated hydrochlorination cycloheptene

Scheme 3. Alumina mediated hydrochlorination of 1-octene

Scheme 4. Mechanism of silica gel or alumina mediated alkene hydrochlorination

Scheme 5. Hydrochlorination of (R)-limonene using SOCl2/SiO2

Scheme 6. Silica-gel mediated hydrochlorination of unactivated alkenes by using 35% hydrochloric acid

Scheme 7. Hydrochlorination of (R)-carvone with great chemoselectivity and regioselectivity

Scheme 8. Hydrochlorination with trimethylchlorosilane and water

Scheme 9. Markovnikov hydrochlorination of olefins with AcCl/EtOH

Scheme 10. Hydrochlorination of alkenes with HCl/DMPU

Scheme 11. Hydrochlorination of alkenes with phosphonium salt

Scheme 12. Hydrochlorination of polyenes with phosphonium salt

Scheme 13. Active reagent and the mechanism of material hydrochlorination

Scheme 14. Two methods of anti-Markovnikov hydrochlorination

Scheme 15. Select examples of the anti-Markovnikov hydrochlorination

Scheme 16. Proposed catalytic cycle for the anti-Markovnikov hydrochlorination of alkenes

Scheme 17. Pt-catalyzed hydrochlorination of alkenes

Scheme 18. Pd-catalyzed hydrochlorination of styrenes

Scheme 19. Mechanism for Pd-catalyzed hydrochlorination of styrenes

Scheme 20. Co-catalyzed hydrochlorination of unactivated alkenes

Scheme 21. Mechanism for Co-catalyzed hydrochlorination

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