Cluster Preface: Silicon in Synthesis and Catalysis

Abstract

Martin Oestreich is Professor of Organic Chemistry at the Technische Universität Berlin. His appointment was supported by the Einstein Foundation Berlin. He received his diploma degree with Paul Knochel (Marburg, 1996) and his doctoral degree with Dieter Hoppe (Münster, 1999). After a two-year postdoctoral stint with Larry E. Overman ­(Irvine, 1999–2001), he completed his habilitation with Reinhard ­Brückner (Freiburg, 2001–2005) and was appointed as Professor of Organic Chemistry at the Westfälische Wilhelms-Universität Münster (2006–2011). He also held visiting positions at Cardiff University in Wales (2005) and at The Australian National University in Canberra (2010). Martin Oestreich’s research focuses on silicon in synthesis and catalysis, the theme of the present SYNLETT Cluster. His early work centered on the use of silicon-stereogenic silicon reagents in asymmetric catalysis, and his laboratory continues to employ them as stereochemical probes in mechanistic investigations. His research group made fundamental contributions to catalytic carbon–silicon bond formation with nucleo­philic and, likewise, electrophilic silicon reagents, and Martin Oestreich is probably best known for his work in silylium-ion chemistry. Recent accomplishments of his laboratory include Friedel–Crafts-type C–H silylation, transfer hydrosilylation, and kinetic resolution of alcohols by enantioselective silylation.

Enantioselective C–H Functionalization toward Silicon-Stereogenic Silanes

“…Due to the inherent properties of the silicon atom (a larger atomic radius compared to carbon atom, a longer C–Si bond compared to C–C bond, easy to form hyper-coordinated intermediates, etc. ), 2 and the poor stability of sp 2 -hybridized silicon atoms (addition reactions for the generation of a silicon-stereogenic center are not feasible), 3 the construction of chiral organosilanes bearing a stereocenter at silicon has always been challenging.…”

Construction of Axial Chirality and Silicon-Stereogenic Center via Rh-Catalyzed Asymmetric Ring-Opening of Silafluorenes

“…It is highly deserved to develop efficient synthetic protocols for the construction of diverse chiral compounds. In recent years, enantiomerically enriched silicon-stereogenic molecules have garnered significant attention, though no natural occurring corresponding compounds have been found. , In contrast to element carbon having stable sp 2 - and sp-hybrid patterns, the silicon atom usually adopts sp 3 -hybrid in nature. To date, catalytic asymmetric syntheses of silicon-stereogenic compounds were all through desymmetrization of prochiral compounds, which could be summarized into two main strategies.…”