Rhodium‐Catalyzed Reaction of Silacyclobutanes with Unactivated Alkynes to Afford Silacyclohexenes

Jin

et al. 2022

Angewandte Chemie

Silanes are important in chemistry and material science. The self-redistribution of HSiCl 3 is an industrial process to prepare SiH 4 , which is widely used in electronics and automobile industries. However, selective silane cross-redistribution to prepare advanced silanes is challenging. We now report an enthalpy-driven silane cross-redistribution to access bis-silanes that contain two different types of SiÀ H bonds in the same molecule. Compared with entropy-driven reactions, the enthalpy-driven reaction shows high regioselectivity, broad substrate scope (62 examples) and high atom economy. Our combined experimental and computational study indicates that the reaction proceeds through a Ni 0 -Ni II -Ni IV catalytic cycle.

Section: Introductionmentioning

confidence: 99%

Nickel‐Catalyzed Cross‐Redistribution between Hydrosilanes and Silacyclobutanes

Jin

et al. 2022

Angewandte Chemie

“…To the best of our knowledge, only Shintani, Hayashi, Nozaki et al and Song have succeeded in forming six-membered tetraorgano-substituted silicon-stereogenic silanes (Fig. 1b ) 39 – 43 , while the construction of Si-chirality on six- and seven-membered triorgano-substituted monohydrosilanes via asymmetric catalysis is still unknown to date, which is presumably due to a lack of general and efficient synthetic methods. Given the increasing demand for the synthesis of novel functional-materials-oriented silicon-bridged biaryls, construction of six- or seven-membered monohydrosilanes in a chiral version is highly attractive.…”

Section: Introductionmentioning

confidence: 99%

Enantioselective construction of six- and seven-membered triorgano-substituted silicon-stereogenic heterocycles

Mai

et al. 2021

Nat Commun

The exploitation of chirality at silicon in asymmetric catalysis is one of the most intriguing and challenging tasks in synthetic chemistry. In particular, construction of enantioenriched mediem-sized silicon-stereogenic heterocycles is highly attractive, given the increasing demand for the synthesis of novel functional-materials-oriented silicon-bridged compounds. Here, we report a rhodium-catalyzed enantioselective construction of six- and seven-membered triorgano-substituted silicon-stereogenic heterocycles. This process undergoes a direct dehydrogenative C−H silylation, giving access to a wide range of triorgano-substituted silicon-stereogenic heterocycles in good to excellent yields and enantioselectivities, that significantly enlarge the chemical space of the silicon-centered chiral molecules. Further elaboration of the chiral monohydrosilane product delivers various corresponding tetraorgano-substituted silicon-stereogenic heterocycles without the loss of enantiopurity. These silicon-bridged heterocycles exhibit bright blue fluorescence, which would have potential application prospects in organic optoelectronic materials.

“…To the best of our knowledge, only Shintani, Hayashi, Nozaki et al and Song have succeeded in forming six-membered tetraorgano-substituted silicon-stereogenic silanes (Fig. 1b) [36][37][38][39][40] , while the construction of Si-chirality on six-and seven-membered triorgano-substituted monohydrosilanes via asymmetric catalysis is still unknown to date, which is presumably due to a lack of general and e cient synthetic methods. Given the increasing demand for the synthesis of novel functional-materials-oriented silicon-bridged biaryls, construction of six-or seven-membered monohydrosilanes in a chiral version is highly attractive.…”

Section: Introductionmentioning

confidence: 99%

Enantioselective Construction of Six- and Seven-Membered Triorgano-Substituted Silicon-Stereogenic Heterocycles

et al. 2020

Preprint

A rhodium-catalyzed enantioselective construction of six- and seven-membered triorgano-substituted silicon-stereogenic heterocycles is developed. This process undergoes a direct dehydrogenative C−H silylation, giving access to a wide range of novel triorgano-substituted silicon-stereogenic heterocycles in good to excellent yields and enantioselectivities, that significantly enlarged the chemical space of the silicon-centered chiral molecules. Further elaboration of the chiral monohydrosilane product delivered various corresponding tetraorgano-substituted silicon-stereogenic heterocycles without the loss of enantiopurity. These novel silicon-bridged heterocycles exhibit bright blue fluorescence, which would have potential application prospects in organic optoelectronic materials.