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http://dx.doi.org/10.1002/anie.201004658 | DOI Listing |
Angew Chem Int Ed Engl
December 2024
Institut für Chemie, Technische Universität Berlin, Strasse des 17. Juni 115, 10623, Berlin, Germany.
A desymmetrizing 1,2-addition of silicon nucleophiles to biaryl derivatives containing an 2,6-dicarbaldehyde-1-yl unit is reported. The reaction is catalyzed by copper with a triazolium-ion-derived N-heterocyclic carbene as the chiral ligand and makes use of an Si-B reagent as the silicon pronucleophile. The practical methodology furnishes axially chiral aromatic carbaldehydes decorated with a centrally chiral α-hydroxysilane moiety in moderate to good yields and with high enantio- as well as excellent diastereoselectivities.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
August 2024
Institut für Chemie, Technische Universität Berlin, Strasse des 17. Juni 115, 10623, Berlin, Germany.
A copper-catalyzed C4-selective addition of silicon nucleophiles released from an Si-B reagent to prochiral pyridinium triflates is reported. The dearomatization proceeds with excellent enantioselectivity using Cu(CHCN)PF as the precatalyst and (R,R)-Ph-BPE (1,2-bis[(2R,5R)-2,5-diphenylphospholan-1-yl]ethane) as the chiral ligand. A carbonyl group at C3 is required for this, likely acting a weak donor group to preorganize and direct the nucleophilic attack towards C4.
View Article and Find Full Text PDFOrg Lett
December 2023
Department of Physics and Chemistry, DGIST, Daegu 42988, Republic of Korea.
A copper-catalyzed chemo- and stereoselective method for the synthesis of ()-2-silyl-1,3-butadienes from a broad range of allenols using mild Si-B reagents is reported in this study. Our protocol required a short reaction time at ambient temperature to produce the desired dienes in high yields. Synthetic applications are highlighted by the one-pot synthesis of tetrasubstituted arylsilanes from allenols as well as the further functionalization of C-Si bonds.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
February 2023
Institut für Chemie, Technische Universität Berlin, Strasse des 17. Juni 115, 10623, Berlin, Germany.
3-Substituted 2H-azirines can be considered strained cyclic ketimines, and highly enantioselective addition reactions of silicon nucleophiles to either acyclic or cyclic ketimines have been elusive so far. The present work closes this gap for those azirines by means of a copper-catalyzed silylation using a silyl boronic ester as a latent silicon nucleophile. The resulting C-silylated, unprotected (N-H) aziridines are obtained in high yields and with excellent enantioselectivities and can be further converted into valuable compounds with hardly any erosion of the enantiomeric excess.
View Article and Find Full Text PDFChemistry
December 2022
Department of Chemistry, Chemistry Institute for Functional Materials, Pusan National University, 46241, Busan, Korea.
Integrating distinct unsaturated C-C systems while simultaneously installing metallic groups has been significantly challenging to execute in a multicomponent reaction. Therefore, designing a suitable mechanistic pathway that provides the required reactivity and selectivity for target C-C bonds with metallic reagents to ensure successful coupling is the key to success. Copper-catalyzed borylallylation and silylallylation have emerged as the most efficient strategies for assembling borylated/silylated skipped (1,4 or 1,5) dienes by catalytically combining an organocopper intermediate with allyl electrophiles.
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