551000-83-0Relevant articles and documents
Scalable Asymmetric Synthesis of the All Cis Triamino Cyclohexane Core of BMS-813160
Deerberg, Joerg,Eastgate, Martin D.,Fan, Yu,Galella, Michael A.,Galindo, Kay A.,González-Bobes, Francisco,Kopp, Nathaniel,La Cruz, Thomas E.,Pathirana, Charles,Sfouggatakis, Chris,Xiao, Yi,Zheng, Bin
, (2021/09/02)
BMS-813160 is a pharmaceutical entity currently in development at Bristol Myers Squibb. Its defining structural feature is a unique chiral all cis triamino cyclohexane core. Medicinal and process chemistry groups at BMS have previously published synthesis
Asymmetric stereodivergent strategy towards aminocyclitols
Trost, Barry M.,Malhotra, Sushant
, p. 8288 - 8292 (2014/07/08)
A concise asymmetric synthesis of aminocyclitols, such as diastereomeric 2-deoxystreptamine analogues and conduramine A, is described. The Pd-catalyzed asymmetric desymmetrization of meso 1,4-dibenzolate enables the synthesis of highly oxidized cyclohexane architectures. These scaffolds can potentially be used to access new aminoglycoside antibiotics and enantiomerically pure α-glucosidase inhibitors.
α-Acyloxynitroso dienophiles in [4+2] hetero Diels-Alder cycloadditions: mechanistic insights
Calvet, Géraldine,Coote, Susannah C.,Blanchard, Nicolas,Kouklovsky, Cyrille
experimental part, p. 2969 - 2980 (2010/06/20)
α-Acyloxynitroso derivatives are a class of heterodienophiles leading to valuable 3,6-dihydro-1,2-oxazines or the corresponding aminoalcohols in good yields. The discovery that a β-oxygenated moiety led to a domino [4+2] cycloaddition/σN-O bond cleavage in the presence of a catalytic amount of Lewis acid was investigated in detail, through kinetic profiling of the reaction both in the absence and presence of a promoter. These studies showed that the role of the Lewis acid was to accelerate the σN-O bond cleavage thereby promoting a highly reproducible sequence. In addition, our preliminary results on an asymmetric version of this domino sequence are reported.
Titanocene(III) chloride-mediated reductions of oxazines, hydroxamic acids, and N-hydroxy carbamates
Cesario, Cara,Tardibono Jr., Lawrence P.,Miller, Marvin J.
experimental part, p. 448 - 451 (2009/04/07)
(Chemical Equation Presented) Titanocene(III) chloride (Cp 2TiCl), generated in situ, reduces N-O bonds of various substrates in good to excellent yields (72-95%). Reactions may be performed with stoichiometric Cp2TiCl or with cataly
Efficient cleavage of the N-O bond of 3,6-dihydro-1,2-oxazines mediated by some α-hetero substituted carbonyl compounds in mild conditions
Galvani, Gilles,Calvet, Geraldine,Blanchard, Nicolas,Kouklovsky, Cyrille
scheme or table, p. 1063 - 1070 (2009/02/05)
The efficient cleavage of the N-O bond of some nitroso Diels-Alder cycloadducts has been achieved in mild conditions, mediated either by 2,2-dimethyl-1,3-dioxan-5-one or 1,3-dithiolane-2-carboxaldehyde. These new and purely organic conditions allow an exc
Reactions of nitroso hetero-Diels-Alder cycloadducts with azides: Stereoselective formation of triazolines and aziridines
Bodnar, Brian S.,Miller, Marvin J.
, p. 3929 - 3932 (2008/02/01)
(Chemical Equation Presented) The addition of azides to acylnitroso hetero-Diels-Alder cycloadducts derived from cyclopentadiene affords exo-triazolines in excellent yield. The reaction is greatly affected by the level of alkene strain, while sterically d
Intermolecular nitroso Diels-Alder cycloaddition of α-acetoxynitroso derivatives in aqueous medium
Calvet, Geraldine,Guillot, Regis,Blanchard, Nicolas,Kouklovsky, Cyrille
, p. 4395 - 4401 (2007/10/03)
The Diels-Alder cycloadditions of the α-acetoxynitroso dienophile 1 in water are reported. The rapid and high yielding synthesis of structurally diverse 3,6-dihydro-1,2-oxazines complements the straightforward elaboration of aminoalcohols obtained from th
Chemokine receptor binding heterocyclic compounds with enhanced efficacy
-
, (2008/06/13)
The invention relates to heterocyclic compounds consisting of a core nitrogen atom surrounded by three pendant groups, wherein two of the three pendant groups are preferably benzimidazolyl methyl and tetrahydroquinolyl, and the third pendant group contains N and optionally contains additional rings. The compounds bind to chemokine receptors, including CXCR4 and CCR5, and demonstrate protective effects against infection of target cells by a human immunodeficiency virus (HIV).
Lewis acid-promoted hetero Diels-Alder cycloaddition of α-acetoxynitroso dienophiles
Calvet, Geraldine,Dussaussois, Marion,Blanchard, Nicolas,Kouklovsky, Cyrille
, p. 2449 - 2451 (2007/10/03)
(Equation Presented) α-Acetoxynitroso compound 3 has been prepared as a new stable, isolable, and reactive dienophile in nitroso Diels-Alder reactions. The yield of the [4 + 2] cycloaddition of α-acetoxynitroso dienophile with 1,3-dienes could be enhanced in the presence of 20 mol % Lewis acid. An unexpected retro hetero-Michael reaction from 26 was observed, leading to the cleavage of the N-O bond of the cycloadduct. This tandem nitroso Diels-Alder/retro hetero-Michael sequence has been used with cyclic and acyclic 1,3-dienes.
α-Chloronitroso compounds derived from carbohydrate ketones: Cycloadditions with cyclic dienes, a synthesis of (-)-physoperuvine and a formal synthesis of (+)-epibatidine
Hall, Adrian,Bailey, Patrick D.,Rees, David C.,Rosair, Georgina M.,Wightman, Richard H.
, p. 329 - 343 (2007/10/03)
1,2-O-Isopropylidene-α-D-xylofuranose 9 was converted into 5-O-(tert-butyldiphenylsilyl)-3-chloro-3-deoxy-1,2-O-isopropylidene-3-C-nitroso- α-o-xylofuranose 17 in four steps, and a similar α-chloronitroso compound 8 was synthesised from 1,2:5,6-di-O-isopropylidene-α-o-glucofuranose 6, the structures of 8 and 17 being confirmed by X-ray crystallography. Reaction of 8 or 17 with cyclohexa-1,3-diene in the presence of small amounts of water gave the cycloadduct (1S,4R)-3-aza-2-oxabicyclo[2.2.2]oct-5-ene, as its hydrochloride (-)-2, in ≥96% ee. Reactions of either 8 or 17 with cyclohepta-1,3-diene similarly gave (1R,5S)-7-aza-6-oxabicyclo[3.2.2]non-8-ene hydrochloride (-)-25 with ≥96% ee, but reactions with cyclopentadiene proceeded differently, with 17 giving the nitrone (E)-(3 R,5 R)-3-[5′-O-(tert-butyldiphenylsilyl)-3′-deoxy-1′,2′-O-is opropylidene-α-D-erythro-pentofuranos-3′-ylidene-amino]-5-chlorocycl opentene N-oxide 19, the structure of which was determined by X-ray crystallography. The dihydrooxazines (-)-25 and (-)-2 were used in syntheses of (-)-physoperuvine (-)-34 and (+)-epibatidine (+)-40, respectively. A pseudoenantiomeric α-chloronitroso compound 51 was also prepared from 2,3-O-isopropylidene-α-L-sorbofuranose 44, and reaction of 51 with cyclohexa-1,3-diene gave (+)-2 with 97% ee.