Stereospecific approaches allow the introduction of a stereogenic center into complex organic molecules using optically active reagents. Among these, the Pd-catalyzed stereospecific cross-coupling of chiral alkylboron compounds stands out as a highly effective tool for organic synthesis. In parallel with advances in the development of borylation technology, the strategy has recently witnessed a growth in its applicability. This account aims to review the progress on Pd-catalyzed stereospecific B-alkyl Suzuki–Miyaura cross-coupling, tracing its evolution from early breakthroughs to the most recent advances. 1 Introduction 2 Cross-Coupling of 1° Alkylboron Compounds 3 Cross-Coupling of Benzylboron Compounds 4 Cross-Coupling of Allyl- and Propargylboron Compounds 5 Cross-Coupling of Other Types of Activated 2° Alkylboron Compounds 6 Cross-Coupling of Unactivated 2° Alkylboron Compounds 7 Conclusion and Outlook
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