Catalytic Asymmetric Construction of Si‐Chiral Silabicyclo[3.3.1]Nonanes Using Functionalized Prochiral Silacyclohexanones
Abstract
ABSTRACT The development of chiral three‐dimensional, sp 3 ‐rich architectures to facilitate the discovery of potent functional molecules is at the forefront of synthetic chemistry. However, facile synthesis of saturated and bridged Si‐chiral silacycles remains elusive due to a lack of pluripotent Si‐prochiral platforms capable of diversity‐oriented asymmetric synthesis. Herein, we report the invention of functionalized prochiral 4,4‐disubstituted silacyclohexanones (FPDSs) as platforms for the modular synthesis of multifunctional sp 3 ‐rich Si‐chiral sila‐bicyclo[3.3.1]nonanes. The FPDS platforms are readily accessible via a newly established tandem S N 2‑substitution/Krapcho‑decarboxylation sequence as a key step to silacyclohexanone core. The utility of FPDS is demonstrated in catalytic asymmetric synthesis of diverse Si‐chiral sila‐bicyclo[3.3.1]nonanes via desymmetric intramolecular aldol reaction, tandem imine formation/Mannich, or Wittig/Michael sequence by chiral enamine catalysis, as well as α‐arylation by cooperative chiral enamine/palladium catalysis. Notably, this represents the first stereoselective method to produce functionalized sp 3 ‐rich Si‐chiral bridged silacycles and the first asymmetric organo/metal cooperative catalysis for forging Si‐chirality.
Article Details
Authors (8)
Zhong‐Tian Ye
Shanghai Engineering Research Center of Molecular Therapeutics and New Drug Development, State Key Laboratory of Molecular & Process Engineering, Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering East China Normal University Shanghai China
Zhong‐Wei Wu
Shanghai Engineering Research Center of Molecular Therapeutics and New Drug Development, State Key Laboratory of Molecular & Process Engineering, Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering East China Normal University Shanghai China
Xi‐Yu Wang
Shanghai Engineering Research Center of Molecular Therapeutics and New Drug Development, State Key Laboratory of Molecular & Process Engineering, Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering East China Normal University Shanghai China
Qiong Xiao
Shanghai Engineering Research Center of Molecular Therapeutics and New Drug Development, State Key Laboratory of Molecular & Process Engineering, Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering East China Normal University Shanghai China
Chuang Ma
Xin Wang
Jian Zhou
Jin‐Sheng Yu
Shanghai Engineering Research Center of Molecular Therapeutics and New Drug Development, State Key Laboratory of Molecular & Process Engineering, Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering East China Normal University Shanghai China