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The synthesis of chiral organosilicon compounds is highly appealing due to their wide and important applications in synthetic chemistry and medicinal science. However, catalytic asymmetric disilylation are surprisingly underrepresented because of the lack of enantioselective methods in the stereoselective control of silyl group transformations. Herein, an asymmetric palladium‐catalyzed disilylation of ether‐tethered aryl iodide contained a styrene moiety through Heck/C−H activation sequence was explored for the first time. Upon high‐throughput screening of TADDOL‐derived phosphoramidites, it was found that L18 is a good match in combination with Pd(dtbpf)Cl2 in the tandem Heck/C−H activation of aryl iodide with hexamethyldisilane to afford disilylated 2.3‐dihydrobenzofunan derivatives in good yields with moderate enantioselectivity. [ABSTRACT FROM AUTHOR]

A novel and unusual palladium‐catalyzed [4+2] annulation of cyclopropenes with benzosilacyclobutanes is reported. This reaction occurred through chemoselective Si−C(sp2) bond activation in synergy with ring expansion/insertion of cyclopropenes to form new C(sp2)−C(sp3) and Si−C(sp3) bonds. An array of previously elusive bicyclic skeleton with high strain, silabicyclo[4.1.0]heptanes, were formed in good yields with excellent diastereoselectivity under mild conditions. An asymmetric version of the reaction with a chiral phosphoramidite ligand furnished a variety of chiral bicyclic silaheterocycle derivatives with good enantioselectivity (up to 95.5:4.5 er). Owing to the mild reaction conditions, the good stereoselectivity profile, and the ready availability of the functionalized precursors, this process constitutes a useful and straightforward strategy for the synthesis of densely functionalized silacycles. [ABSTRACT FROM AUTHOR]

A unique 1,3-dipolar [3+2] cycloaddition of alkyl 4-oxo-4-arylbut-2-enoates bearing two different electron-withdrawing groups was completed by using the silver/(R)-DTBM-Segphos catalyst system, which gives the corresponding fully substituted pyrrolidines with four stereogenic centers in good yields and with excellent enantioselectivities (up to 98% ee). [ABSTRACT FROM AUTHOR]

• Swollen-induced in-situ encapsulation of catalysts in cross-linked polysiloxane elastomers polymer. • Silicone rubber-based microchannel reactor was employed for asymmetric transforms. • Cross-linked polysiloxane elastomers was proved to be easily recycled by filtration or pick-up,reused by several times and exhibits excellent enantioselectivities 94–96% ees The immobilization of molecular catalysts to fabricate heterogeneous catalysts for catalytic asymmetric transformations is extremely important and has attracted great attentions. Herein we developed a simple and new strategy for the heterogenization of homogeneous molecular complexes into the cross-linked polymer. It is demonstrated for the first time that the cross-linked polysiloxane elastomers can be applied for the swollen-induced in-situ encapsulation of homogeneous catalysts with or without chiral ligands. The swollen-induced in-situ encapsulation of silver catalyst system in the cross-linked polysiloxane elastomers led to the formation of silicone rubber-based hierarchically porous that could be used in asymmetric [3+2] cycloaddition, asymmetric tandem conjugate addition−elimination reaction and oxidation of hydrosilanes to silanols. The swollen-induced in-situ encapsulation of chiral silver complex in the cross-linked polysiloxane elastomers was proved to be easily recycled by filtration or pick-up and reused by several times. The simplest heterogeneous catalysis by the strategy of swollen-induced in-situ encapsulation can be extended to the encapsulation of chiral metal catalysts into different polymeric materials for the heterogenization of homogeneous catalysis. [Display omitted] [ABSTRACT FROM AUTHOR]

Catalytic asymmetric variants for functional group transformations based on carbon-carbon bond activation still remain elusive. Herein we present an unprecedented palladium-catalyzed (3 + 2) spiro-annulation merging C(sp 2 )-C(sp 2 ) σ bond activation and click desymmetrization to form synthetically versatile and value-added oxaspiro products. The operationally straightforward and enantioselective palladium-catalyzed atom-economic annulation process exploits a TADDOL-derived bulky P-ligand bearing a large cavity to control enantioselective spiro-annulation that converts cyclopropenones and cyclic 1,3-diketones into chiral oxaspiro cyclopentenone-lactone scaffolds with good diastereo- and enantio-selectivity. The click-like reaction is a successful methodology with a facile construction of two vicinal carbon quaternary stereocenters and can be used to deliver additional stereocenters during late-state functionalization for the synthesis of highly functionalized or more complex molecules., Competing Interests: The authors declare no competing interests., (This journal is © The Royal Society of Chemistry.)

A novel and unusual palladium-catalyzed [4+2] annulation of cyclopropenes with benzosilacyclobutanes is reported. This reaction occurred through chemoselective Si-C(sp 2 ) bond activation in synergy with ring expansion/insertion of cyclopropenes to form new C(sp 2 )-C(sp 3 ) and Si-C(sp 3 ) bonds. An array of previously elusive bicyclic skeleton with high strain, silabicyclo[4.1.0]heptanes, were formed in good yields with excellent diastereoselectivity under mild conditions. An asymmetric version of the reaction with a chiral phosphoramidite ligand furnished a variety of chiral bicyclic silaheterocycle derivatives with good enantioselectivity (up to 95.5:4.5 er). Owing to the mild reaction conditions, the good stereoselectivity profile, and the ready availability of the functionalized precursors, this process constitutes a useful and straightforward strategy for the synthesis of densely functionalized silacycles., (© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)