1034094-54-6Relevant articles and documents
Direct Synthesis of α-Allenols from TMS-Protected Alkynes and Aldehydes Mediated by Tetrabutylammonium Fluoride
Huang, Xiaojun,Bugarin, Alejandro
supporting information, p. 12696 - 12700 (2016/08/30)
A unique chemoselective synthesis of α-allenic alcohols is presented. Tetrabutylammonium fluoride (TBAF) mediated this transformation under mild reaction conditions. A range of functional groups is well-tolerated in this reaction, while affording adducts
Beyond classical reactivity patterns: Hydroformylation of vinyl and allyl arenes to valuable β- And γ-aldehyde intermediates using supramolecular catalysis
Dydio, Pawe?,Detz, Remko J.,De Bruin, Bas,Reek, Joost N. H.
supporting information, p. 8418 - 8429 (2014/06/24)
In this study, we report on properties of a series of rhodium complexes of bisphosphine and bisphosphite L1-L7 ligands, which are equipped with an integral anion binding site (the DIM pocket), and their application in the regioselective hydroformylation of vinyl and allyl arenes bearing an anionic group. In principle, the binding site of the ligand is used to preorganize a substrate molecule through noncovalent interactions with its anionic group to promote otherwise unfavorable reaction pathways. We demonstrate that this strategy allows for unprecedented reversal of selectivity to form otherwise disfavored β-aldehyde products in the hydroformylation of vinyl 2- and 3-carboxyarenes, with chemo- and regioselectivity up to 100%. The catalyst has a wide substrate scope, including the most challenging substrates with internal double bonds. Coordination studies of the catalysts under catalytically relevant conditions reveal the formation of the hydridobiscarbonyl rhodium complexes [Rh(Ln)(CO)2H]. The titration studies confirm that the rhodium complexes can bind anionic species in the DIM binding site of the ligand. Furthermore, kinetic studies and in situ spectroscopic investigations for the most active catalyst give insight into the operational mode of the system, and reveal that the catalytically active species are involved in complex equilibria with unusual dormant (reversibly inactivated) species. In principle, this involves the competitive inhibition of the recognition center by product binding, as well as the inhibition of the metal center via reversible coordination of either a substrate or a product molecule. Despite the inhibition effects, the substrate preorganization gives rise to very high activities and efficiencies (TON > 18‰000 and TOF > 6000 mol mol-1 h-1), which are adequate for commercial applications.
Supramolecular control of selectivity in hydroformylation of vinyl arenes: Easy access to valuable β-aldehyde intermediates
Dydio, Pawel,Reek, Joost N. H.
supporting information, p. 3878 - 3882 (2013/05/09)
Go against the flow! A rationally designed regioselective hydroformylation catalyst, [Rh/L], in which noncovalent ligand-substrate interactions allow the unprecedented reversal of selectivity from the typical α-aldehyde to the otherwise unfavored product β-aldehyde, is reported. This catalytic system opens up novel and sustainable synthetic pathways to important intermediates for the fine-chemicals industry.
