138566-91-3Relevant articles and documents
Iron(II)-Catalyzed Intermolecular Aminofluorination of Unfunctionalized Olefins Using Fluoride Ion
Lu, Deng-Fu,Zhu, Cheng-Liang,Sears, Jeffrey D.,Xu, Hao
, p. 11360 - 11367 (2016)
We herein report a new catalytic method for intermolecular olefin aminofluorination using earth-abundant iron catalysts and nucleophilic fluoride ion. This method tolerates a broad range of unfunctionalized olefins, especially nonstyrenyl olefins that are incompatible with existing olefin aminofluorination methods. This new iron-catalyzed process directly converts readily available olefins to internal vicinal fluoro carbamates with high regioselectivity (N vs F), many of which are difficult to prepare using known methods. Preliminary mechanistic studies demonstrate that it is possible to exert asymmetric induction using chiral iron catalysts and that both an iron-nitrenoid and carbocation species may be reactive intermediates.
A one-pot preparation of allylsilanes and (Z)-alk-2-enylsilanes
Desponds, Olivier,Franzini, Livia,Schlosser, Manfred
, p. 150 - 152 (1997)
Metalation of alk-1-enes, using the mixture of butyllithium and potassium tert-butoxide in tetrahydropyran, followed by stereohomogenization and ultimate treatment with chlorotrimethylsilane afforded a series of alk-2-enyltrimethylsilanes in good yield and with (Z/E) ratios ranging from 95:5 to 98:2. The deprotonation of propene can be rapidly and readily accomplished with a stoichiometric amount of the superbase suspended in pentane on a 1 mol scale.
4-AMINO OR 4-ALKOXY-SUBSTITUTED ARYL SULFONAMIDE COMPOUNDS WITH SELECTIVE ACTIVITY IN VOLTAGE-GATED SODIUM CHANNELS
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Page/Page column 71-72, (2020/07/05)
Disclosed are compounds of Formula (I), Formula (II), or a salt thereof: Formula (I) Formula (II) which compounds have properties for inhibiting Nav 1.7 ion channels found in peripheral and sympathetic neurons. Also described are pharmaceutical formulations comprising the compounds of Formula (I), Formula (II) or their salts, and methods of treating pain disorders, cough, and itch using the same.
Silicon Grignard Reagents as Nucleophiles in Transition-Metal-Catalyzed Allylic Substitution
Xue, Weichao,Oestreich, Martin
, p. 233 - 239 (2019/01/04)
A broad range of transition-metal catalysts is shown to promote allylic substitution reactions of allylic electrophiles with silicon Grignard reagents. The procedure was further elaborated for CuI as catalyst. The regioselectively is independent of the leaving group for primary allylic precursors, favoring α over γ. The stereochemical course of this allylic transposition was probed with a cyclic system, and anti -dia-stereoselectivity was obtained.
Synthesis and reactions of donor cyclopropanes: efficient routes to cis- and trans-tetrahydrofurans
Dunn, Jonathan,Dobbs, Adrian P.
supporting information, p. 7386 - 7414 (2015/08/24)
Abstract A detailed study on the synthesis and reactions of silylmethylcyclopropanes is reported. In their simplest form, these donor-only cyclopropanes undergo Lewis acid promoted reaction to give either cis- or trans-tetrahydrofurans, with the selectivity being reaction condition-dependant. The adducts themselves are demonstrated to be an important scaffold for structural diversification. The combination of a silyl-donor group in a donor-acceptor cyclopropane with novel acceptor groups is also discussed.
Catalysis and chemodivergence in the interrupted, formal homo-nazarov cyclization using allylsilanes
Shenje, Raynold,Williams, Corey W.,Francois, Katherine M.,France, Stefan
supporting information, p. 6468 - 6471 (2015/02/05)
A chemodivergent, Lewis acid catalyzed allylsilane interrupted formal homo-Nazarov cyclization is disclosed. With catalytic amounts of SnCl4 and in the presence of allyltrimethylsilane, a formal Hosomi-Sakurai-type allylation of the oxyallyl cation intermediate is observed. A variety of functionalized donor-acceptor cyclopropanes and allylsilanes were shown to be amenable to the reaction transformation and the allyl products were formed in up to 92% yield. Under dilute reaction conditions with stoichiometric SnCl4 and at reduced temperatures, an unusual formal [3 + 2]-cycloaddition between the allylsilane and the oxyallyl cation occurred to give hexahydrobenzofuran products in up to 69% yield.
Donor cyclopropanes in synthesis: Utilising silylmethylcyclopropanes to prepare 2,5-disubstituted tetrahydrofurans
Dunn, Jonathan,Motevalli, Majid,Dobbs, Adrian P.
scheme or table, p. 6974 - 6977 (2012/02/13)
The use of donor-only silylmethylcyclopropanes in the Lewis acid promoted reaction with aldehydes to generate 2,5-disubstituted tetrahydrofurans is described. The diastereoselectivity obtained in the product is very much dependent upon the temperature of
Mesoporous aluminosilicate-catalyzed allylation of carbonyl compounds and acetals
Ito, Suguru,Hayashi, Akira,Komai, Hirotomo,Yamaguchi, Hitoshi,Kubota, Yoshihiro,Asami, Masatoshi
supporting information; body text, p. 2081 - 2089 (2011/04/19)
A mesoporous aluminosilicate (Al-MCM-41) was found to be an effective heterogeneous catalyst for the reaction of both carbonyl compounds and acetals with allylsilanes to afford the corresponding homoallyl silyl ethers and homoallyl alkyl ethers, respectively. Both the mesoporous structure and the presence of aluminum moiety were indispensable for the high catalytic activity of Al-MCM-41. Moreover, Al-MCM-41 could catalyze the reaction of acetals chemoselectively in the presence of the corresponding carbonyl compounds. The solid acid catalyst Al-MCM-41 could be recovered easily by filtration and could be reused three times without a significant loss of catalytic activity.
Mechanistic study on the base-promoted reaction of allylphenylsilanes to alkenylsilanols
Imazeki, Shigeaki,Sugawara, Hiroo,Sano, Atsunori,Akiyama, Takahiko
experimental part, p. 623 - 629 (2009/04/11)
On treatment of allylphenylsilanes with t-BuOK and 18-crown-6 in DMSO, isomerization of the olefinic double bond and subsequent substitution of the phenyl group with a hydroxy group took place smoothly to afford alkenylsilanol derivatives in good yields. The reaction mechanism was investigated using 18O-labeled sulfoxide. We found that a (methylsulfinyl)methyl anion generated from DMSO participated in this reaction.
Allene: As small in size as versatile in synthesis. A general scope of its use-fulness as a C3-synthon for carbocyclic annulations
Barbero, Asuncion,Pulido, Francisco J.
, p. 779 - 785 (2007/10/03)
Allenes react with silylcuprates leading to allyl- or vinylsilanes depending on the structure of the allene and the nature of the silylcuprate. The silyl group used and temperature conditions can also influence the final outcome. Reversibility is a common
