Silicon-Mediated Organic Synthesis

Abstract

Organic chemists have used the chemical properties of tetracovalent silicon in a remarkable variety of new synthetic transformations. In carbon-functional silanes, exceptional stabilization is provided to a carbocation center in the beta position when the carbon-silicon bond lies in plane. This phenomenon directs electrophilic attack to the silicon-substituted carbon in aryl-, vinyl-, and alkynylsilanes and to carbon-3 in allylsilanes. For different reasons, silicon also stabilizes a carbon-metal bond in the alpha position. Consequently, access to many silicon-containing organometallics is readily available. The exceptional strength of silicon-oxygen and silicon-fluorine bonds is yet another factor that controls the chemical reactivity of silicon reagents. In recent developments, preparative chemists have taken advantage of these properties in imaginative and useful ways.

Evolution of Cobalt Catalysis for Catalytic Construction of Si‐H ‐Containing Semi‐Penetrating Networks: Updated Application in Nanosilver‐Catalyzed Alkynylation of Paraformaldehyde

“…We believed that Si−H –containing organosilicon materials would be an important support in heterogeneous catalysis. Notably, present work provided a good example for the organosilicon‐mediated organic synthesis (SiMOS) . Studies are ongoing to gain insight into the relationship between organosilicon‐based structures and properties of the organosilicon materials and expanding its applications to heterogeneous catalysis and green chemistry.…”

Co-Complexes Derived from Alkene Insertion to Alkyne-Dicobaltpentacarbonyl Complexes: Insight into the Regioselectivity of Pauson−Khand Reactions of Cyclopropenes

“…Ring-opened product 10 contains a carbon-metal bond that is α-to the trimethylsilyl group that was originally bound to the cyclopropane moiety of 13 . Silicon is known to stabilize α-carbon-metal bonds 16. This stability may be reflected in a relatively low barrier for the transformation of 13 into 10 , and provide a plausible explanation for the susceptibility of 13 to undergo reductive cleavage.…”

Organosilicon-Mediated Organic Synthesis (SiMOS): A Personal Account

“…4 In fact, since the 1970s, organosilicon chemistry has played an important role in organic synthesis and catalysis, especially as a protecting group, which allows the use of organosilicon compounds in the development of new functional compounds. 5 Especially in the past decades, organosilicon compounds found important and new applications in organic synthesis, such as the effective application of organosilicon compounds in the transition-metal-catalyzed cross-coupling reactions, the syntheses and application of silicon-stereogenic organosilicon compounds, the siliconcontaining organocatalysts or chiral ligands, silicon-based Lewis acids in catalytic organic transformation, and the use of silanes and its functional materials as stoichiometric reductants in a range of chemo-, stereo-, and enantioselective catalytic reductions. 6 Undoubtedly, the unabated growth of applications of organosilicon compounds and related materials in the resolution of synthetic problems has continued.…”

“…8 Thus the apparent size of a silyl group is much larger than the corresponding all-carbon alkyl group. As a result of these properties, it is envisaged that continuous developments have been included as a greater emphasis on the application of 'organosilicon-mediated organic synthesis (SiMOS)' 5,9 with excellent activity and stereoselectivity in new reactions or supplementary to those performed with traditional catalytic methods with environmentally benign approaches. As part of our working hy-pothesis on SiMOS, we initially explored the application of organosilicon compounds in the synthesis of structurally diverse molecules through different approaches.…”