1408075-90-0Relevant articles and documents
C-H Insertion via Ruthenium Catalyzed gem-Hydrogenation of 1,3-Enynes
Fürstner, Alois,Gutiérrez González, Alejandro,Leutzsch, Markus,Peil, Sebastian
supporting information, p. 4158 - 4167 (2022/03/03)
gem-Hydrogenation of an internal alkyne with the aid of [Cp*RuCl]4 as the precatalyst is a highly unorthodox transformation, in which one C atom of the triple bond is transformed into a methylene group, whereas the second C atom gets converted into a ruthenium carbene. In the case of 1,3-enynes bearing a propargylic steering substituent as the substrates, the reaction occurs regioselectively, giving rise to vinyl carbene complexes that adopt interconverting η1/η3-binding modes in solution; a prototypical example of such a reactive intermediate was characterized in detail by spectroscopic means. Although both forms are similarly stable, only the η3-vinyl carbene proved kinetically competent to insert into primary, secondary, or tertiary C-H bonds on the steering group itself or another suitably placed ether, acetal, orthoester, or (sulfon)amide substituent. The ensuing net hydrogenative C-H insertion reaction is highly enabling in that it gives ready access to spirocyclic as well as bridged ring systems of immediate relevance as building blocks for medicinal chemistry. Moreover, the reaction scales well and lends itself to the formation of partly or fully deuterated isotopologues. Labeling experiments in combination with PHIP NMR spectroscopy (PHIP = parahydrogen induced polarization) confirmed that the reactions are indeed triggered by gem-hydrogenation, whereas kinetic data provided valuable insights into the very nature of the turnover-limiting transition state of the actual C-H insertion step.
THIENOPYRIDINE CARBOXAMIDES AS UBIQUITIN-SPECIFIC PROTEASE INHIBITORS
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, (2017/09/05)
The disclosure relates to inhibitors of USP28 and/or USP25 useful in the treatment of cancers, inflammation, autoimmune diseases, and infectious diseases, having the Formula (I), where R1, R2, R3, R4, R5, R5', R6, R7, X, m, and n are described herein.
Skeletal diversification via heteroatom linkage control: Preparation of bicyclic and spirocyclic scaffolds from N-substituted homopropargyl alcohols
Painter, Thomas O.,Bunn, Jonathon R.,Schoenen, Frank J.,Douglas, Justin T.,Day, Victor W.,Santini, Conrad
, p. 3720 - 3730 (2013/06/05)
The discovery and application of a new branching pathway synthesis strategy that rapidly produces skeletally diverse scaffolds is described. Two different scaffold types, one a bicyclic iodo-vinylidene tertiary amine/tertiary alcohol and the other, a spirocyclic 3-furanone, are each obtained using a two-step sequence featuring a common first step. Both scaffold types lead to intermediates that can be orthogonally diversified using the same final components. One of the scaffold types was obtained in sufficiently high yield that it was immediately used to produce a 97-compound library.
