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4.4.7.2.1.1 Transition-Metal-Catalyzed Silaboration

DOI: 10.1055/sos-SD-104-00395

Delvos, L. B.; Oestreich, M.Science of Synthesis Knowledge Updates, (2017177.

The palladium-catalyzed, Z-selective silaboration of terminal alkynes 26 with regioselective borylation at the terminus of the triple bond is known for several silylboron reagents presented in Section 4.4.7.1.[‌35‌,‌38‌,‌44‌,‌45‌,‌47‌] Among these, the reaction procedure using [di­meth­yl(phenyl)silyl]pinacolborane (19) shows broadest applicability, mainly owing to the high stability of the pinacolborane group (Scheme 20).[‌45‌,‌47‌] The transformation proceeds highly regio- and stereoselectively with catalytic amounts of palladium(II) acetate and 1,1,3,3-tetramethylbutyl isocyanide as ligand in refluxing toluene to generate (2-silylvinyl)boronic esters 27 in good yields. The B—C bond is formed exclusively at the terminal carbon atom of the triple bond in a formal syn addition. The substrate scope includes a variety of functionalized alkyl substituents as well as conjugated C=C and C=O groups. Aryl substituents as R1 groups were investigated in less detail.

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M8 M8 Meeee (88/88) Meeeee (%) Mee
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M8 Meeee (88/88) Meeeee (%) Mee
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M8 Meeee (88/88) Meeeee (%) Mee
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References


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