Research Progress in Transition Metal-Catalyzed Asymmetric Hydroboration of 1,1-Disubstituted Alkenes

doi:10.6023/cjoc202603032

Abstract

Asymmetric hydroboration of alkenes is one of the important methods for the efficient construction of chiral boron- containing compounds. Over the past few decades, with the development of a series of privileged ligands, significant progress has been made in the transition metal catalyzed asymmetric hydroboration of 1,1-disubstituted alkenes. This review systematically summarizes the current research status of this field, with a focus on the existing catalytic systems and reaction mechanisms, identifies the current challenges, and provides an outlook on future development prospects.

Key words: hydroboration, 1,1-disubstituted alkenes, transition metal catalysis, asymmetric catalysis

Cite this article

Kangyu Xiong, Zhan Lu. Research Progress in Transition Metal-Catalyzed Asymmetric Hydroboration of 1,1-Disubstituted Alkenes[J]. Chinese Journal of Organic Chemistry, 2026, 46(7): 2493-2510.

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Fig. & Tab. 19

Scheme 1. Enantioselective control of asymmetric hydroboration of 1,1-disubstituted alkenes

Scheme 2. Rhodium-catalyzed asymmetric hydroboration of 1,1-disubstituted aryl alkenes

Scheme 3. Rhodium-catalyzed asymmetric hydroboration of directing group-substituted 1,1-disubstituted alkenes

Scheme 4. Iridium-catalyzed asymmetric hydroboration of 1,1-disubstituted aryl alkenes

Scheme 5. Copper-catalyzed asymmetric protoboration of 1,1-disubstituted aryl alkenes

Scheme 6. Copper-catalyzed asymmetric 1,2-hydroboration of 1,3-dienes

Scheme 7. Cobalt-catalyzed asymmetric hydroboration of 1,1-disubstituted aryl alkenes

Scheme 8. Cobalt-catalyzed asymmetric hydroboration of 1,1-disubstituted sterically hindered aryl alkenes

Scheme 9. Cobalt-catalyzed asymmetric 1,2-hydroboration of 1,3-dienes

Scheme 10. Cobalt-catalyzed asymmetric hydroboration/cyclization of remote enynes

Scheme 11. Cobalt-catalyzed asymmetric hydroboration of ester-substituted 1,1-disubstituted alkenes

Scheme 12. Cobalt-catalyzed asymmetric hydroboration of silyl-substituted 1,1-disubstituted aryl alkenes

Scheme 13. Cobalt-catalyzed asymmetric hydroboration of silyl ether-substituted 1,1-disubstituted aryl alkenes

Scheme 14. Cobalt-catalyzed asymmetric hydroboration of cyclopropyl-substituted 1,1-disubstituted aryl alkenes

Scheme 15. Cobalt-catalyzed asymmetric hydroboration of trifluoromethyl-substituted 1,1-disubstituted aryl alkenes

Scheme 16. Cobalt-catalyzed asymmetric hydroboration of unstrained cyclic ether-substituted 1,1-disubstituted aryl alkenes

Scheme 17. Iron-catalyzed asymmetric hydroboration of cyclopropyl-substituted 1,1-disubstituted aryl alkenes

Scheme 18. Asymmetric hydroboration of unactivated 1,1-disubstituted alkenes

Metal	Catalytically active species	Chirality-controlling step	C—B bond formation step	Representative references
Rh	B-Rh-H	Alkene migratory insertion into Rh-H	B-Rh-C reductive elimination	[18], [27], [29-30]
Ir	B-Ir-H	Alkene migratory insertion into Ir-H	B-Ir-C reductive elimination	[32]
Cu	Cu-H	Alkene migratory insertion into Cu-H	σ-Bond metathesis between the Cu-C species and pinacol borane	[55-56]
Cu	Cu-B	Alkene migratory insertion into Cu-B and enantioselective Cu-C protonation	Alkene migratory insertion into Cu-B	[34]
Co	Co-H	Alkene migratory insertion into Co-H Alkene migratory insertion into Co-C'	σ-Bond metathesis between the Co-C species and pinacol borane	[39-41] [45]
	B-Co-H	Alkene migratory insertion into Co-H	B-Co-C reductive elimination	[43]
	B-Co-H	Alkene migratory insertion into Co-B	Alkene migratory insertion into Co-B	[47]
Fe	Fe-H	Alkene migratory insertion into Fe-H β-C Elimination of the Fe-C species	σ-Bond metathesis between the Fe-C species and pinacol borane	[53] [54]

Table 1. Transition metal-catalyzed asymmetric hydroboration modes of 1,1-disubstituted alkenes

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