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. 2019 Mar 4;10(15):4177-4184.
doi: 10.1039/c9sc00078j. eCollection 2019 Apr 21.

Highly selective palladium-catalyzed one-pot, five-fold B-H/C-H cross coupling of monocarboranes with alkenes

Yunjun Shen  1 , Kang Zhang  1 , Xuewei Liang  1 , Rakesh Dontha  1 , Simon Duttwyler  1
Affiliations

Highly selective palladium-catalyzed one-pot, five-fold B-H/C-H cross coupling of monocarboranes with alkenes

Yunjun Shen et al. Chem Sci. .

Abstract

Palladium-catalyzed dehydrogenative B-H/C-H cross coupling of monocarborane anions with alkenes is reported, allowing for the first time the isolation of selectively penta-alkenylated boron clusters. The reaction cascade is regioselective for the cage positions, leading directly to B2-6 functionalization. Under mild and convenient conditions, styrenes, benzylic alkenes and aliphatic alkenes are demonstrated to be viable coupling partners with exclusive vinyl-type B-C bond formation. Multiple subsequent transformations provide access to directing group-free products, chiral derivatives and penta-alkylated cages. The five-fold coupling, combined with the latter reactions, represents a powerful methodology for the straightforward synthesis of new classes of boron clusters.

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Figures

Fig. 1
Fig. 1. (a) Previously reported metal-catalyzed functionalization of {CB11} cages and (b) regioselective dehydrogenative penta-alkenylation by direct B–H/C–H cross coupling.
Fig. 2
Fig. 2. X-ray crystal structures of (a) 3b and (b) 4b (cations, solvent molecules and styryl H atoms omitted for clarity, 30% displacement ellipsoids).
Scheme 1
Scheme 1. Synthesis of chiral 3u/v and 4u/v; curved arrows around R* indicate identical sense of absolute configuration.
Scheme 2
Scheme 2. Reduction of the double bond.
Fig. 3
Fig. 3. (a) 11B{1H} NMR spectrum and (b) X-ray crystal structure of palladium complex 1c–Pd (cation and H atoms omitted for clarity; 30% displacement ellipsoids).
Scheme 3
Scheme 3. Putative selective β-hydride elimination to explain the regioselectivity of double bond formation with benzyl and alkyl substrates.
See this image and copyright information in PMC

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