89008-80-0Relevant articles and documents
The Silicon-Hydrogen Exchange Reaction: Catalytic Kinetic Resolution of 2-Substituted Cyclic Ketones
List, Benjamin,Zhang, Pinglu,Zhou, Hui
supporting information, p. 1953 - 1956 (2021/11/17)
We have recently reported the strong and confined, chiral acid-catalyzed asymmetric 'silicon-hydrogen exchange reaction'. One aspect of this transformation is that it enables access to enantiopure enol silanes in a tautomerizing σ-bond metathesis, via deprotosilylation of ketones with allyl silanes as the silicon source. However, until today, this reaction has not been applied to racemic, 2-substituted, cyclic ketones. We show here that these important substrates readily undergo a highly enantioselective kinetic resolution furnishing the corresponding kinetically preferred enol silanes. Mechanistic studies suggest the fascinating possibility of advancing the process to a dynamic kinetic resolution.
Asymmetric Induction via a Helically Chiral Anion: Enantioselective Pentacarboxycyclopentadiene Br?nsted Acid-Catalyzed Inverse-Electron-Demand Diels-Alder Cycloaddition of Oxocarbenium Ions
Gheewala, Chirag D.,Hirschi, Jennifer S.,Lee, Wai-Hang,Paley, Daniel W.,Vetticatt, Mathew J.,Lambert, Tristan H.
supporting information, p. 3523 - 3527 (2018/03/21)
An enantioselective catalytic inverse-electron-demand Diels-Alder reaction of salicylaldehyde acetal-derived oxocarbenium ions and vinyl ethers to generate 2,4-dioxychromanes is described. Chiral pentacarboxycyclopentadiene (PCCP) acids are found to be effective for a variety of substrates. Computational and X-ray crystallographic analyses support the unique hypothesis that an anion with point-chirality-induced helical chirality dictates the absolute sense of stereochemistry in this reaction.
The 2-(2-Azidoethyl)cycloalkanone strategy for bridged amides and medium-sized cyclic amine derivatives in the Aubé-Schmidt reaction
Macleod, Fraser,Lang, Stuart,Murphy, John A.
supporting information; experimental part, p. 529 - 534 (2010/10/02)
2-(2-Azidoethyl)cycloalkanones afford bridged lactams in the Aubé-Schmidt reaction, sometimes in excellent yield, and solvolysis yields derivatives of medium-ring amines. Attempts to divert the Schmidt reaction with an arene-mediated fragmentation of the normal Schmidt intermediate have led to an initial example. Georg Thieme Verlag Stuttgart.