Unsaturated organoboron and organosilicon compounds constitute an important class of organometallic compounds, which due to the presence of silyl- or boryl- group attached to Csp2 atoms, their simple and straightforward transformations in coupling and demetallation reactions, found a broad range of applications in the synthesis of fine chemicals or new materials with tailored properties. Such compounds might be synthesized in many transformations but two of them: hydrometallation and Marciniec coupling reactions permitted to obtain compounds with high effectivity, selectivity, and in the case of hydrometallation reactions with excellent atom economy. Most of these processes occur in a homogeneous phase, which ensures excellent yields and stereo- and regioselectivity. On the other hand, such conditions generate problems with catalyst reuse, product separation, and substantial consumption of toxic, volatile organic solvents. According to the assumptions of sustainable development in chemistry, the new procedures, which allow to intensify the process in terms of its efficiency, according to green chemistry rules are of prior importance in modern chemical industry. In this manuscript, the newest achievements in the application of green solvents (ionic liquids, liquid polymers, and supercritical CO2) in catalytic hydrometallation of alkynes and coupling of vinylmetalloids with olefins are discussed. Such an approach builds a new strategy for effective catalyst immobilization and its reuse, the increase of process productivity by the application of repetitive batch processes, and elimination of organic solvents, typically used in these transformations. Selected contributions in this field of chemistry are presented within this review.
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