107733-62-0Relevant academic research and scientific papers
Amination of(η3-allyl)dicarbonylnitrosyliron complexes: A route to γ- amino-α,β-unsaturated carboxylic acid derivatives
Nakanishi, Saburo,Okamoto, Kenji,Yamaguchi, Hiroshi,Takata, Toshikazu
, p. 1735 - 1741 (1998)
Amines reacted regioselectively with (ν3-allyl)dicarbonylnitrosyliron complexes having ester group on the allyl ligand to give γ-amino-α,β- unsaturated esters in high yields. A remarkable effect of the substituents attached to the allyl ligand was observed on the reaction rate and regioselectivity of the amination. The methoxycarbonyl group significantly accelerates the reaction rate and enhances the regioselectivity of the reaction. The phenyl group retards the reaction, but enhances the regioselectivity, while alkyl groups retard the reaction and diminish the regioselectivity.
Synthesis of Cyclic Guanidines via Silver-Catalyzed Intramolecular Alkene Hydroamination Reactions of N-Allylguanidines
Garlets, Zachary J.,Silvi, Mattia,Wolfe, John P.
, p. 2331 - 2334 (2016)
The silver-catalyzed hydroamination of tosyl-protected N-allylguanidines is described. These reactions provide substituted cyclic guanidines in high yields. The reactions are amenable to the construction of quaternary stereocenters as well as both monocyc
Unexpected Rearrangement of N-Allyl-2-phenyl-4,5-Dihydrooxazole-4-Carboxamides to Construct Aza-Quaternary Carbon Centers
Choi, Goyeong,Jo, Seoyoung,Mun, Juyeon,Jeong, Yonguk,Kim, Seok-Ho,Jung, Jong-Wha
, (2019/12/25)
The unexpected rearrangement of N-allyl-2-phenyl-4,5-dihydrooxazole-4-carboxamides in the presence of LiHMDS has been found. The key features are: (1) the net reaction consisted of 1,3-migration of the N-allyl group, (2) the rearrangement produced a congested aza-quaternary carbon center, (3) both cyclic and acyclic substrates underwent the unexpected rearrangement to afford products in moderate to high yields, and (4) the reaction seemed to be highly stereoselective. In addition, a plausible mechanism has been discussed.
Synthesis of N?H Bearing Imidazolidinones and Dihydroimidazolones Using Aza-Heck Cyclizations
Xu, Feiyang,Shuler, Scott A.,Watson, Donald A.
, p. 12081 - 12085 (2018/09/11)
The synthesis of unsaturated, unprotected imidazolidinones via an aza-Heck reaction is described. This palladium-catalyzed process allows for the cyclization of N-phenoxy ureas onto pendant alkenes. The reaction has broad functional group tolerance, can b
A Simple, Broad-Scope Nickel(0) Precatalyst System for the Direct Amination of Allyl Alcohols
Sweeney, Joseph B.,Ball, Anthony K.,Lawrence, Philippa A.,Sinclair, Mackenzie C.,Smith, Luke J.
supporting information, p. 10202 - 10206 (2018/08/06)
The preparation of allylic amines is traditionally accomplished by reactions of amines with reactive electrophiles, such as allylic halides, sulfonates, or oxyphosphonium species; such methods involve hazardous reagents, generate stoichiometric waste streams, and often suffer from side reactions (such as overalkylation). We report here the first broad-scope nickel-catalysed direct amination of allyl alcohols: An inexpensive NiII/Zn couple enables the allylation of primary, secondary, and electron-deficient amines without the need for glove-box techniques. Under mild conditions, primary and secondary aliphatic amines react smoothly with a range of allyl alcohols, giving secondary and tertiary amines efficiently. This “totally catalytic” method can also be applied to electron-deficient nitrogen nucleophiles; the practicality of the process was demonstrated in an efficient, gram-scale preparation of the calcium antagonist drug substance flunarizine (Sibelium).
3,3-Dimethoxypropylsulfonyl Group: A new versatile protecting and activating group for amine synthesis
Sakamoto, Izumi,Iwaoka, Kazuya,Kawada, Yuta,Naito, Takanori,Makida, Kazuyoshi,Takeuchi, Yuki,Nishii, Takeshi,Horikawa, Mitsuyo,Kaku, Hiroto,Tsunoda, Tetsuto
, p. 3052 - 3060 (2018/05/23)
3,3-Dimethoxypropylsulfonyl (Dimps) chloride was prepared and used as a new versatile sulfonating agent for ammonia, primary and secondary amines to afford corresponding Dimps-amides in excellent yields. The resulting N-nonsubstituted and N-monosubstituted Dimps-amides, activated amines, were alkylated satisfactorily under new Mitsunobu conditions. The Dimps group was removed by treatment in aqueous solution under acidic followed by basic conditions. Furthermore, epilachnene, the defensive droplets from the Mexican bean beetle, Epilachna varivestis, was synthesized utilizing this Dimps methodology in short steps.
Benign catalysis with iron: Unique selectivity in catalytic isomerization reactions of olefins
Jennerjahn, Reiko,Jackstell, Ralf,Piras, Irene,Franke, Robert,Jiao, Haijun,Bauer, Matthias,Beller, Matthias
experimental part, p. 734 - 739 (2012/06/04)
The use of noble metal catalysts in homogeneous catalysis has been well established. Due to their price and limited availability, there is growing interest in the substitution of such precious metal complexes with readily available and bio-relevant catalysts. In particular, iron is a "rising star" in catalysis. Herein, we present a general and selective iron-catalyzed monoisomerization of olefins, which allows for the selective generation of 2-olefins. Typically, common metal complexes give mixtures of various internal olefins. Both bulk-scale terminal olefins and functionalized terminal olefins give the corresponding products under mild conditions in good to excellent yields. The proposed reaction mechanism was elucidated by in situ NMR studies and supported by DFT calculations and extended X-ray absorption fine structure (EXAFS) measurements.
2-(1,3-Dioxan-2-yl)ethylsulfonyl group: A new versatile protecting and activating group for amine synthesis
Sakamoto, Izumi,Izumi, Norimasa,Yamada, Taeko,Tsunoda, Tetsuto
, p. 71 - 74 (2007/10/03)
(Chemical Equation Presented) 2-(1,3-Dioxan-2-yl)ethylsulfonyl (Dios) chloride was synthesized and used as a new versatile sulfonating agent for amines. Primary and secondary amines were sulfonated very easily in excellent yields with Dios chloride. N-Nonsubstituted and N-monosubstituted Dios-amides, activated amines, were alkylated satisfactorily under new Mitsunobu conditions utilizing (cyanomethylene)tributylphosphorane (CMBP). The Dios group is very stable under basic and reductive conditions and is removed by heating in a hot aqueous solution of trifluoroacetic acid.
Thermal and catalyzed [3,3]-phosphorimidate rearrangements
Chen, Bin,Mapp, Anna K.
, p. 6712 - 6718 (2007/10/03)
[3,3]-Sigmatropic rearrangements have been widely utilized for the synthesis of structurally complex organic molecules because of the ease with which carbon-carbon bonds are formed in a regio-and stereocontrolled manner. However, there are far fewer [3,3]-rearrangements available for the selective formation of carbon-nitrogen bonds despite the enormous potential of such reactions for the preparation of stereodefined allylic amines. We describe here the scope and mechanism of a [3,3]-rearrangement of allylic phosphorimidates that provides access to stereodefined allylic amines of diverse structure. The reactive intermediate in the reaction, an allylic phosphorimidate, is produced in situ through the combination of readily available starting materials (allylic alcohols, chlorophosphites, and organic azides), rendering the reaction an efficient three-component process. Analogous to other [3,3]-rearrangements, the stereochemistry in an allylic alcohol starting material is transferred with fidelity to the allylic amine product and, further, allylic amines are produced as single olefin isomers. In addition, a crossover experiment indicates that the rearrangement is an intramolecular process. Finally, activation of the allylic moiety either through incorporation of electron-deficient functional groups or through the use of a transition-metal catalyst significantly facilitates the reaction and consequently the preparation of a wider range of substitution patterns.
Lewis Acid Mediated [2,3]-Sigmatropic Rearrangement of Allylic α-Amino Amides
Blid, Jan,Brandt, Peter,Somfai, Peter
, p. 3043 - 3049 (2007/10/03)
Boron trifluoride and BBr3 mediated [2,3]-sigmatropic rearrangements of allylic α-amino amides have been developed affording secondary amines in good yields. (E)-Crotyl and (E)-cinnamyl α-amino amides 2b and 2c exhibit excellent syn-diastereoselectivity upon rearrangement with either Lewis acid. The allylic amine 2a forms upon treatment with BF 3 or BBr3 a five-membered heterocylic complex in which a single halide anion has been displaced by the carbonyl oxygen atom. The structures of the Lewis acid-amine complexes were elucidated using NMR spectroscopy. A plausible reaction mechanism, based on DFT calculations, is presented. Thus, BF3- or BBr3-complexed allylic amines 2 are shown to preferentially proceed, after deprotonation, via an endo transition state.
