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Synthesis 2025; 57(03): 495-521
DOI: 10.1055/a-2343-0780
DOI: 10.1055/a-2343-0780
review
Directing-Group-Assisted Transition-Metal-Catalyzed Selective BH Functionalization of o-Carboranes
Financial support from the Research Grants Council of the Hong Kong Special Administration Region (Project No. 14305420 to JZ), the Shenzhen Science and Technology Program (Project No. QTD20221101093558015 to ZX), and the National Natural Science Foundation of China (Project No. 22331005 to ZX) are gratefully acknowledged.
Abstract
Carboranes are a type of molecular clusters consisting of carbon, hydrogen, and boron atoms. They possess unique characteristics, such as three-dimensional aromaticity, icosahedral geometry, and robustness. Functionalized carboranes have been utilized in various fields, including medicine, materials, and organometallic/coordination chemistry. In this context, selective functionalization of o-carboranes has received tremendous attention, specifically in the regio- and enantioselective modification of the ten chemically similar BH vertices within the carborane cage. In recent years, significant progress has been made in catalytic vertex-specific BH functionalization, as well as achieving enantioselective functionalization of the cage BH. This review provides an overview of the recent advancements in this research field.
1 Introduction
2 Carboxy-Assisted BH Functionalization
2.1 Formation of B–C Bonds
2.2 Formation of B–N Bonds
2.3 Formation of B–O Bonds
2.4 Formation of B–X Bonds
2.5 Consecutive Formation of B–C and B–Y (Y = N, O) Bonds
3 N-Based Directing-Group-Assisted B–H Functionalization
3.1 Acylamino as a Directing Group
3.2 Amide as a Directing Group
3.3 Pyridyl as a Directing Group
3.4 Imine as a Directing Group
4 Phosphinyl-Assisted Cage B–H Functionalization
5 Bidentate-Directing-Group-Assisted B–H Functionalization
6 Other Directing-Group-Assisted B–H Functionalization
7 Conclusions
Publikationsverlauf
Eingereicht: 06. Mai 2024
Angenommen nach Revision: 11. Juni 2024
Accepted Manuscript online:
11. Juni 2024
Artikel online veröffentlicht:
15. Juli 2024
© 2024. Thieme. All rights reserved
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