14506-32-2Relevant articles and documents
Scandium trifluoromethanesulfonate, a novel catalyst for the addition of allyltrimethylsilane to aldehydes
Aggarwal, Varinder K.,Vennall, Graham P.
, p. 3745 - 3746 (1996)
Scandium triflate (2-10 mol%) has been found to be a highly efficient catalyst for the addition of allyltrimethylsilane to both aromatic and aliphatic aldehydes.
Carbonyl allylation of aldehydes catalyzed by a silica-supported poly-γ-diphenylarsinopropylsiloxane palladium(0) complex
Cai, Mingzhong,Huang, Yizheng,Zhao, Hong,Zhang, Rongli
, p. 2436 - 2440 (2004)
A silica-supported poly-γ-diphenylarsinopropylsiloxane palladium (0) complex has been prepared from γ-chloropropyltriethoxysilane via immobilization on fumed silica, followed by reacting with potassium diphenylarsenide and palladium chloride, and then the reduction with hydrazine hydrate. The palladium(0) complex has been found to catalyze the allylation of aldehydes via the formation of π-allylpalladium complexes, using allylic chlorides as allylating agent and SnCl2 as reducing agent. This polymeric palladium complex can be recovered and reused.
Weaker lewis acid, better catalytic activity: Dual mechanisms in perfluoroarylborane-catalyzed allylstannation reactions
Morrison, Darryl J.,Piers, Warren E.
, p. 2857 - 2860 (2003)
(Matrix is presented) PhB(C6F5)2 exhibits much higher activity as a Lewis acid catalyst for the allylstannation of aromatic aldehydes than the stronger Lewis acid B(C6F 5)3. This anomalous enhancement of catalytic activity for the weaker LA is shown to be partly due to decreased thermodynamic stability of ion pair 2b relative to 2a in the product-forming step of the reaction. A mechanistic path where the borane serves as the true LA catalyst is more important for the weakly Lewis acidic borane.
Allylation reactions of carbonyl compounds using an organosilicon reagent in aqueous media
Aoyama, Naohiro,Hamada, Tomoaki,Manabe, Kei,Kobayashi, Shu
, p. 676 - 677 (2003)
Allylation reactions of carbonyl compounds such as aldehydes and reactive ketones using allyltrimethoxysilane in aqueous media proceeded smoothly in the presence of 5 mol% of a CdF2-terpyridine complex; the presence of the ligand plays an impor
Simple Modular Synthetic Approaches to Asymmetric NN'N'', NN' C, or NN' P -Type Amido Pincer Ligands: Synthesis, Characterisation, and Preliminary Ligation Studies
Herasymchuk, Khrystyna,Huynh, Jennifer,Lough, Alan J.,Roces Fernández, Laura,Gossage, Robert A.
, p. 2121 - 2129 (2016)
A simple modular approach is presented which has been directed towards the synthesis of potentially monoanionic NN'N'', NN'C, and NN'P pincer-type ligands. These pincers incorporate an amide functionality derived from the skeletal structure of readily available 2-(2-aminophenyl)-4,5-dioxooxazoles. All of the pincers are synthesized in moderate yields (up to 74%) and are characterised by nuclear magnetic spectroscopy (NMR), elemental analyses, and infrared (IR) spectroscopy. X-ray crystallography is also performed on the chiral and achiral alkyl halide precursors and on an oxide derivative of a pincer with a NN'P-atom donor set. A palladium derivative of one of the NN'N''-pincers is shown to be an active catalyst for the addition of an allyl group to various benzaldehydes using n-Bu3Sn(allyl) as allyl source.
Palladium-catalyzed coupling of allyl acetates with aldehyde and imine electrophiles in the presence of bis(pinacolato)diboron
Sebelius, Sara,Wallner, Olov A.,Szabo, Kalman J.
, p. 3065 - 3068 (2003)
(Matrix presented) An efficient one-pot procedure was developed for palladium-catalyzed electrophilic substitution of allyl acetates (2a-h) in the presence of bis(pinacolato)diboron (1). These reactions proceed with an excellent regioselectivity and with a remarkably high stereoselectivity. The catalytic transformations take place via palladium-catalyzed formation of allyl boronates, which subsequently react with aldehyde (3) and sulfon-imine (4) electrophiles to afford homoallylic alcohols (5a-h) and amines (6a-d), respectively. A particularly interesting mechanistic feature is that the allylic substitution of the transient allyl boronate with sulfon-imine requires palladium catalysis. This finding indicates that the formation of the homoallylic amine derivatives (6a-d) involves bis-allylpalladium intermediates.
Organocatalytic Asymmetric Synthesis of Cyclic Acetals with Spirooxindole Skeleton
Shikari, Amit,Mandal, Koushik,Chopra, Deepak,Pan, Subhas Chandra
supporting information, p. 58 - 63 (2021/11/09)
An organocatalytic asymmetric synthesis of cyclic acetal with spirooxindole skeleton has been developed via a domino reaction between isatin and γ-hydroxy enones. Bifunctional squaramide catalyst with adamantyl motif was found to be the most effective for the cascade reaction. With 10 mol% of the catalyst, the desired products were obtained in 1.8:1 to 9:1 diastereo- and 86% to >99% enantioselectivities from a range of substituted isatins and γ-hydroxy enones. (Figure presented.).
A chiral oxazoline for catalytic enantioselective Nozaki-Hiyama-Kishi allylation and vinylation of aldehydes
Chen, Chinpiao,Kumbhar, Sharad V.
, (2020/09/22)
Asymmetric allylation and vinylation of aldehydes with allyl halides and vinyl halides have been achieved using the chromium(II)-oxazoline catalyst. The catalyst promotes the highly efficient enantioselective Nozaki–Hiyama-Kishi (NHK) allylation of aldehydes using allyl bromide, producing the corresponding homoallylic alcohols in good yields (up to 84%) and a high level of enantioselectivity (up to 98% ee). Meanwhile, the NHK vinylation of aldehydes produce desired allylic alcohols in satisfactory yields (up to 88%) and a high level of enantioselectivity (up to 97% ee). We developed a reliable and milder protocol for preparing chiral homoallylic and allylic alcohols.
MnO2as a terminal oxidant in Wacker oxidation of homoallyl alcohols and terminal olefins
Fernandes, Rodney A.,Ramakrishna, Gujjula V.,Bethi, Venkati
, p. 6115 - 6125 (2020/10/27)
Efficient and mild reaction conditions for Wacker-type oxidation of terminal olefins of less explored homoallyl alcohols to β-hydroxy-methyl ketones have been developed by using a Pd(ii) catalyst and MnO2 as a co-oxidant. The method involves mild reaction conditions and shows good functional group compatibility along with high regio- and chemoselectivity. While our earlier system of PdCl2/CrO3/HCl produced α,β-unsaturated ketones from homoallyl alcohols, the present method provided orthogonally the β-hydroxy-methyl ketones. No overoxidation or elimination of benzylic and/or β-hydroxy groups was observed. The method could be extended to the oxidation of simple terminal olefins as well, to methyl ketones, displaying its versatility. An application to the regioselective synthesis of gingerol is demonstrated.
