The insertion of phenyl(bromodichloromethyl)mercury-derived dichlorocarbene into the SiC(ring) and βCH bonds of the cis and trans isomers of 1,3-dimethyl-1-n-butyl-1-silacyclobutane

Harnessing the β-Silicon Effect for Regioselective and Stereoselective Rhodium(II)-Catalyzed C–H Functionalization by Donor/Acceptor Carbenes Derived from 1-Sulfonyl-1,2,3-triazoles

“…Seyferth and coworkers first showed that phenyl(bromo-dichloromethyl)mercury-derived dichlorocarbene inserts regioselectively into the β position of a variety of tetraalkylsilanes (Scheme 1a). 13 This work unveiled the delicate balance of sterics and electronics around the silicon which can favorably dispose carbene insertion into the β position of silicon. Migita and coworkers later showed that photolysis of acceptor/acceptor carbenes in the presence of tetraalkylsilanes could also achieve β C-H functionalization, although the regioselectivity was poor (Scheme 1b).…”

“…Prior efforts directed toward the intermolecular functionalization of organosilicon compounds by C–H insertion reactions with carbenes focused on establishing highly regioselective reactions (Scheme ). Seyferth and co-workers first showed that phenyl­(bromo-dichloromethyl)­mercury-derived dichlorocarbene inserts regioselectively into the β position of a variety of tetraalkylsilanes (Scheme a) . This work unveiled the delicate balance of sterics and electronics around the silicon which can favorably dispose carbene insertion into the β position of silicon.…”

Site-Selective Molecular Transformation: Acylation of Hydroxy Groups and C–H Amination

“…Although the β-silicon effect is an established concept in synthetic organic chemistry, prior investigation into the β-silicon effect in intermolecular C-H functionalization reactions has mainly focused on carbene insertion reactions. [125][126][127][128][129][130][131][132] Based on this background, we investigated β-silicon-effect-promoted intermolecular site-selective C(sp 3 )-H amination reactions. 133) The reaction of triethylsilylbenzene 51a gave desired primary C(sp 3 )-H aminated product 52a in an intermolecular manner, despite using an excess amount of the substrate (Chart 14).…”

Darstellung und Eigenschaften von und Reaktionen mit metallhaltigen Heterocyclen, XLVII [1]. Einschiebungsreaktionen von phasentransferkatalytisch in situ erzeugten Dihalocarbenen in P-haltige Manganacycloalkane – Struktur und chemisches Verhalten der Reaktionsprodukte / Preparation and Properties of and Reactions with Metal-Containing Heterocycles, XLVII [1]. Insertion Reactions of Phase-Transfer-Catalytically in situ Generated Dihalocarbenes into P-Containing Manganacycloalkanes – Structure and Chemical

“…Schwefel, Schwefeldioxid und Selen reagieren mit Metallacyclobutanen, deren Metall ein Element der vierten Hauptgruppe darstellt, unter Ringerweiterung [2]. Dihalocarbene setzen sich mit gespannten Ringsystemen sowohl unter Ringerweiterung als auch unter Insertion in die ß-C-H-Bindung um [2,3,6]. Bei fünf-und sechsgliedrigen Sila-, Germa-und Stannacycloalkanen tritt der zuletzt genannte Fall ausschließlich ein [4,5].…”