3514-86-1Relevant academic research and scientific papers
Iron(II)-catalyzed chlorolactamization of γ,δ-unsaturated carboxylic acids
Kluegge, Jan,Herdtweck, Eberhardt,Bach, Thorsten
, p. 1199 - 1202 (2004)
A one-pot chlorolactamization of γ,δ-unsaturated carboxylic acids is presented. Substrates like carboxylic acid 1 were transformed into the acyl azides which upon treatment with FeCl2 and TMSCl in i-PrOH cyclized to yield lactams such as 2 (75%
Visible-Light-Mediated Synthesis of Amidyl Radicals: Transition-Metal-Free Hydroamination and N-Arylation Reactions
Davies, Jacob,Svejstrup, Thomas D.,Fernandez Reina, Daniel,Sheikh, Nadeem S.,Leonori, Daniele
supporting information, p. 8092 - 8095 (2016/07/16)
The development of photoredox reactions of aryloxy-amides for the generation of amidyl radicals and their use in hydroamination-cyclization and N-arylation reactions is reported. Owing to the ease of single-electron-transfer reduction of the aryloxy-amides, the organic dye eosin Y was used as the photoredox catalyst, which results in fully transition-metal-free processes. These transformations exhibit a broad scope, are tolerant to several important functionalities, and have been used in the late-stage modification of complex and high-value N-containing molecules.
FeCl2-catalyzed intramolecular chloroamination reactions
Danielec, Holger,Kluegge, Jan,Schlummer, Bjoern,Bach, Thorsten
, p. 551 - 556 (2007/10/03)
2-Alkenyloxycarbonyl azides 1 and 2-alkynyloxycarbonyl azides 3 undergo in the presence of trimethylsilyl chloride and catalytic amounts of FeCl 2 an intramolecular chloroamination (aminochlorination) reaction (Procedure 1). The corresponding o
Inversion of the direction of stereoinduction in the coupling of chiral γ,δ-unsaturated fischer carbene complexes with o-ethynylbenzaldehyde
Ghorai, Binay K.,Menon, Suneetha,Lee Johnson, Dennis,Herndon, James W.
, p. 2121 - 2124 (2007/10/03)
(matrix presented) A variety of γ,δ-unsaturated carbene complexes that feature a stereogenic center at the β-carbon couple with 2-ethynylbenzaldehyde to afford hydrophenanthrene derivatives with a high degree of stereoinduction. The direction of stereoinduction is opposite for examples where the stereogenic center is acyclic vs examples where it is within a ring.
Development of efficient new methodology for generation, cyclization and functional trapping of iminyl and amidyl radicals
Lin, Xichen,Artman III, Gerald D.,Stien, Didier,Weinreb, Steven M.
, p. 8779 - 8791 (2007/10/03)
New methodology has been devised for the generation and subsequent cyclization of iminyl and amidyl radicals under mild conditions. The process involves either the treatment of oximes with 2,6-dimethylbenzenesulfinyl chloride, or the treatment of hydroxamic acids with tert-butylsulfinyl chloride (-50°C to rt), to give the corresponding nitrogen radicals, followed by cyclization onto pendant olefins. Radical traps such as diphenyl diselenide, diphenyl disulfide, and TEMPO can be used to terminate the cyclizations, thus introducing functionality that provides multiple options for further manipulation. In a more convenient procedure, both iminyl and amidyl radical cyclizations can be initiated using commercially available diethyl chlorophosphite which generally provides similar (with diphenyl disulfide and TEMPO) or significantly higher (with diphenyl diselenide) yields of products.
Ring opening of cyclopropane in tricyclo[4.3.0.02,9]nonan-3-one with electrophile-nucleophile reagents
Fernandez-Mateos, A.,Alonso, J. J. Perez,Gonzales, R. Rubio
, p. 847 - 860 (2007/10/03)
Four tricyclo[4.3.0.02,9]nonan-3-one systems were treated with TBDMSI, TMSTFA and TMSTFA/NaSPh, affording different cyclopropane cleavage products, depending on the location of the substituent and the nature of the reagent.
Synthesis and Reactions of Iodo Lactams
Knapp, Spencer,Levorse, Anthony T.
, p. 4006 - 4014 (2007/10/02)
The synthesis of a series of iodo lactams has been achieved by a new cyclization method that depends on generating N,O-bis(trimethylsilyl)imidate derivatives as intermediates.Treatment of an unsaturated amide with trimethylsilyl triflate in pentane and then iodine in tetrahydrofuran gives the iodo lactam.Some reactions of this new difunctional group with bases, nucleophiles, and Michael acceptors leading to functionalized or elaborated lactams are presented.In general, iodo lactams undergo direct SN2 reactions with reactive (but weakly basic) nucleophiles like azide and triphenylphosphine and elimination or decomposition in the presence of bases or basic nucleophiles.Sodium hydride may be used to generate an N-acylaziridine intermediate, which can be opened with azide to deliver an azido lactam with overall retention of stereochemistry.Silver-assisted solvolysis of iodo lactams gives the hydroxy lactams with retention of configuration, probably also because of participation by the lactam nitrogen.The sodium salt of 5-(iodomethyl)-2-pyrrolidinone (3), generated at -20 deg C, undergoes an annulation reaction with unsaturated esters (but not sulfones), leading to pyrrolizidine derivatives.
Synthesis of Oxindole Derivatives from N-Alkenyl-o-Chloroanilides with Zero-Valent Nickel Complex
Canoira, L.,Rodriguez, J. G.
, p. 1511 - 1518 (2007/10/02)
Oxindole derivatives have been obtained from N-alkenyl-o-chloroanilides by reaction with tetrakis(triphenylphoaphine)nickel(0) in toluene as solvent in good yields.A detailed analysis of all the products of the reaction allows to confirm the postulated mechanism of the cyclization reaction.The o-chloroanilides of the 3-cyclohexenylacetic acid fails in the cyclization reaction, since the torsional hindrance seems to avoid that the endocyclic double bond may be orthogonally to the ortho-?-nickel complex intermediate on the aromatic ring.
Synthesis of Indole Derivatives from N-Alkenyl-o-chloroanilines with Zero-valent Nickel Complex
Rodriguez, J. G.,Canoira, L.
, p. 883 - 888 (2007/10/02)
Reaction of N-alkenyl-o-chloroanilines in toluene with tetrakis(triphenylphosphine)nickel(0) was carried out mainly to give indole and indoline derivatives in good yields.A detailed analysis of the reaction products has been done and it allows us to confirm the postulated mechanism of the cyclization reaction.Torsional hindrance around C-C-Csp2 bond seems to prevent the cyclization reaction.
