16488-43-0Relevant articles and documents
Heterolytic (2 e) vs Homolytic (1 e) Oxidation Reactivity: N?H versus C?H Switch in the Oxidation of Lactams by Dioxirans
Annese, Cosimo,D'Accolti, Lucia,Fusco, Caterina,Licini, Giulia,Zonta, Cristiano
supporting information, p. 259 - 262 (2017/01/17)
Dioxiranes are powerful oxidants that can act via two different mechanisms: 1) homolytic (H abstraction and oxygen rebound) and 2) heterolytic (electrophilic oxidation). So far, it has been reported that the nature of the substrate dictates the reaction mode independently from the dioxirane employed. Herein, we report an unprecedented case in which the nature of the dioxirane rules the oxidation chemoselectivity. In particular, a switch from C?H to N?H oxidation is observed in the oxidation of lactams moving from dimethyl dioxirane (DDO) to methyl(trifluoromethyl)dioxirane (TFDO). A physical organic chemistry study, which combines the oxidation with two other dioxiranes methyl(fluoromethyl)dioxirane, MFDO, and methyl(difluoromethyl)dioxirane, DFDO, with computational studies, points to a diverse ability of the dioxiranes to either stabilize the homo or the heterolytic pathway.
Cascade cyclization triggered by imine formation. Formal synthesis of the alkaloid (±)-stemoamide and its 9a-epimer
Brito, Gilmar A.,Sarotti, Ariel M.,Wipf, Peter,Pilli, Ronaldo A.
supporting information, p. 6664 - 6668 (2016/01/28)
A concise formal synthesis of stemoamide (1) and its 9a-epimer 14 in 5 steps is described featuring a cascade cyclization triggered by imine formation. A good selectivity for either epimer is readily accomplished by variation of the ester (9b or 9a, respectively) and the reaction conditions.
COMPOUNDS AND METHODS FOR PRODUCING A CONJUGATE
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Paragraph 00427-00428, (2014/05/24)
The present disclosure provides conjugate structures and compound structures used to produce these conjugates. Also provided are methods of producing drug-polypeptide or detectable label-polypeptide conjugates linked through a modified amino acid. Structures of the modified amino acids used in producing the conjugates are disclosed.
Oxidative cleavage of lactams in water using dioxiranes: An expedient and environmentally-safe route to ω-nitro acids
Annese, Cosimo,D'Accolti, Lucia,Filardi, Rosella,Tommasi, Immacolata,Fusco, Caterina
, p. 515 - 517 (2013/02/23)
By taking advantage of the appreciable stability of dioxiranes in water, a safe yet efficient route to ω-nitro acids by oxidation of lactams of various ring sizes under mild conditions has been reported. In essentially all the cases examined, reactions proceed selectively to afford products in remarkably high yields (up to 99%) and with high purity (94-99%). Also, an interesting example of higher reaction selectivity in water than in organic solvent (acetonitrile) is discussed.
Enantioselective henry addition of methyl 4-nitrobutyrate to aldehydes. Chiral building blocks for 2-pyrrolidinones and other derivatives
Blay, Gonzalo,Hernandez-Olmos, Victor,Pedro, Jose R.
supporting information; experimental part, p. 3058 - 3061 (2010/08/19)
A catalytic highly enantioselective Henry addition of methyl 4-nitrobutyrate to aldehydes using a Cu(II)-amino pyridine complex as catalyst is described. The products resulting from this reaction constitute a new, highly versatile family of chiral buildin
Syntheses of new 1 → (2 + 1) C-branched monomers for the construction of multifunctional dendrimers
Newkome, George R.,Kim, Hyung J.,Moorefield, Charles N.,Maddi, Hima,Yoo, Kyung-Soo
, p. 4345 - 4354 (2007/10/03)
For the purpose of providing a route to multifunctionalized dendrimers, new types of 1 → (2 + 1) C-branched monomers, possessing either ester and protected hydroxy groups or mixed esters, were designed and synthesized. Thus, di-tert-butyl 4-(3-[X]oxypropyl)-4-aminoheptanedionate (X = MeCO, 4; X = CH2CH2CN, 6; X = CH2C6H5, 7) was prepared in high yields via the protection of the nitro precursor 2(X = H), which was readily accessible from the Michael addition of 4-nitrobutanol with tert-butyl acrylate, followed by catalytic reduction. These monomers were readily attached to an appropriate four-directional core to produce the first-generation dendrimers (e.g., 9-11). The related second-generation dendrimer (15), possessing two different functional groups on both the surface and interior, was convergently synthesized from monomer 3. Alternatively, the mixed ester 17 was prepared starting with benzyl 4-nitrobutanoate (16); selective deprotection offered access to the representative 1 → (2 + 1) C-branched monomer 20, which was converted to dendrimers 29 and 30 with a single novel terminus per dendron. These 1 → (2 + 1) C-branched monomers offer synthetic versatility to place different functionality at different levels within or on the surface of the dendritic construct.
PROTEASE INHIBITORS
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Page/Page column 25-28, (2008/06/13)
This invention relates in general to certain substituted 3,7-dioxoazepan-4-ylamides of Formula (1) which are protease inhibitors.
Heterobicyclic and tricyclic nitric oxide synthase inhibitors
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, (2015/09/24)
The current invention discloses useful bicyclic and tricyclic amidino derivative compounds, pharmaceutical compositions containing these novel compounds, and to their use as nitric oxide synthase inhibitors.
Enantioselective synthesis of 3-hydroxypiperidin-2-ones
Gibbs, Gary,Hateley, Martin J.,McLaren, Lee,Welham, Matthew,Willis, Christine L.
, p. 1069 - 1072 (2007/10/03)
An efficient synthesis of (S)- and (R)-3-hydroxypiperidin-2-ones from methyl 5-nitro-2-oxopentanoate is described. A one-pot enzyme catalysed hydrolysis of the ester and reduction of the ketone gave enantiopure 2- hydroxy-5-nitropentanoic acids which on esterification, catalytic hydrogenation over a platinum(IV) oxide catalyst and intramolecular: cyclisation gave the target compounds in 93% overall yield and >99% ee.
Preparation of alkyl-substituted indoles in the benzene portion. Part 5. Efficient preparative procedure for 4-substituted indole derivatives
Fuji,Muratake,Natsume
, p. 2338 - 2343 (2007/10/02)
An effective and short synthetic method for 4-substituted indole derivatives was developed based on the two sequential reactions, i.e. nucleophilic addition of carbanions to common precursor molecules, 3-(1,3-dioxolan-2-yl)-1-[1(phenylsulfonyl)- and 1-[(4
