Transition-metal-catalyzed silylmetalation of acetylenes and its application to the stereoselective synthesis of steroidal side chains

CuI/Pd0 Cooperative Dual Catalysis: Tunable Stereoselective Construction of Tetra‐Substituted Alkenes

“…Although the first example was reported by Oshima et al. in 1983,8 this methodology was only revisited in 2011, by Loh et al 9. Generally, these β‐silyl alkenyl carbonyl compounds are still being accessed by means of the hydrosilylation of electron‐deficient alkynes by using ruthenium catalysts 10.…”

Copper(I)‐Catalyzed Regioselective Addition of Nucleophilic Silicon Across Terminal and Internal Carbon–Carbon Triple Bonds

“…Silicon‐based cuprates are reagents of choice to achieve that transformation,2 and (R 3 Si) 2 CuLi⋅LiCN used to be the standard source of the silicon nucleophile 3. Protocols catalytic in copper rely on either R 3 SiMgMe4 or (R 3 Si) 2 Zn5 as precursors of anionic silicon 6. Zincates R 3 SiZnR 2 Li and (R 3 Si) 3 ZnLi in the presence of a copper catalyst7 as well as novel dianion‐type zincates R 3 SiZnR(OR) 2 Mg 2 Cl alone8 do also transfer silicon groups onto carbon–carbon triple bonds.…”

Silylmetalation of Alkenes

“…Although transition-metal-catalyzed addition of a nonanionic silyl reagent to alkenes, for example, in hydrosilylation, [1] bis-silylation, [2] silylstannylation, [3] and silylboration, [4] is relatively facile and well-developed, addition of an anion-ic silyl reagent, such as silylcopper and silylzinc complexes, to alkenes has been difficult, due mainly to the low reactivity of alkenes. Indeed, there are plenty of examples of silylmetalation of alkynes, [5][6][7][8][9][10][11] allenes, [12,13] and 1,3-dienes, [14,15] but few in the case of alkenes. Carbometalation is also of great interest, and much effort has been directed towards this tough task, although the situation is much the same as with silylmetalation.…”