A Simple Indirect Route for the Synthesis of N-Alkyl-4-imino-1,4-dihydro-2H-3,1-benzoxazin-2-ones (original) (raw)
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Tetrahedron Letters, 2000
Reaction of 3-arylimino-2-indolinones 1 with m-chloroperbenzoic acid in CH 2 Cl 2 or methanol at 0 C leads to the corresponding 3-aryl-2,4(1H,3H)-quinazolinediones 4 and (2-arylcarbamoyphenyl)carbamic acid methyl ester 5, respectively. These conversions proceed through 4-arylimino-(1H,4H)-3,1-benzoxazin-2-one 2 and its ring-opened isocyanate carboxamide isomer 3 as key intermediates. # The synthesis of 3-aryl-2,4-quinazolinediones are of current interest from both pharmacological and chemical aspects. 1 These compounds are prepared by various methods. 2 Most of these methods involve rearrangement of dierent starting materials. 3 Recently, we have reported the preparation of 3-arylimino-2-indolinones 1 and their applications for the synthesis of several types of heterocyclic systems. 4 As a continuation of this work, we wish to report the rearrangement and mechanism of the formation of 3-aryl-2,4(1H,3H)-quinazolinediones 4 from oxidation of isatin-3-imines 1 with m-chloroperbenzoic acid (m-CPBA).
Novel 1,4-benzoxazine derivatives were synthesized by an efficient and simple method in high yields. Readily available starting materials, operational simplicity, mild reaction conditions and novelty are the key advantages of this method. The synthetically attractive feature of the procedure is reflected by its applicability to a wide range of isatin and aniline derivatives. Besides their novel structures, these compounds may have important biological activities and industrial applications. Furthermore, we demonstrated that in BaeyereVilliger oxidation reaction, the phenyl group migrate better than amidine groups but not as good as amide group. The migratory ability for these groups in BaeyereVilliger oxidation reaction is ranked amide > phenyl > amidine.
Synthesis and reactions of 1-hydroxy-9,9a-dihydro-1 H-imidazo[1,2- a]indol-2-(3 H)-ones
Tetrahedron, 2011
a b s t r a c t 1-Hydroxy-9,9a-dihydro-1H-imidazo[1,2-a]indol-2(3H)-ones, as a new type of azaheterocyclic hydroxamic acids, have been synthesized regioselectively from 1-carbamoylmethyl-or 1-(methoxycarbonyl) methyl-2,3,3-trimethyl-3H-indolium salts by reaction with hydroxylamine in the presence of a strong base. The alkylation and reduction with sodium borohydride of these novel heterocycles have been investigated. When treated with protic acids 1-hydroxy-or 1-alkoxy-9,9a-dihydro-1H-imidazo[1,2-a]indol-2(3H)-ones underwent ring opening of the imidazolidine to afford 1-[2-(hydroxyamino)-2-oxoethyl]-2,3,3-trimethyl-3H-indolium salts. The structural assignments are based on extensive 1 H, 13 C and 15 N NMR spectroscopic studies and single crystal X-ray analyses.
Tetrahedron Letters, 2011
The Journal of Organic Chemistry, 2008
The parent 5H-indazolo[3,2-b]benzo[d]-1,3-oxazine heterocycle as well as a series of novel analogues have been synthesized utilizing two subsequent intramolecular heterocyclizations in one pot. A variety of diversity groups were added to explore the scope of this reaction and to provide a number of new compounds for biological screening. Wang, L.; Caldwell, C. G.; Chen, P.; Finke, P. E.; Oates, B.; MacCoss, M.; Mills, S. G.; Malkowitz, L.; Gould, S. L.; DeMartino, J. A.; Springer, M. S.; Hazuda, D.; Miller, M.; Kessler, J.; Danzeisen, R.; Carver, G.; Carella, A.; Holmes, K.; Lineberger, J.; Schleif, W. A.; Emini, E. A. Bioorg. Med. Chem. Lett. 2001, 11, 3103-3106. (4) Goodman, K. B.; Cui, H.; Dowdell, S. E.; Gaitanopoulos, D. E.; Ivy, R. L.; Sehon, C. A.; Stavenger, R. A.; Wang, G. Z.; Viet, A. Q.; Xu, W.; Ye, G.; Semus, S. F.; Evans, C.; Fries, H. E.; Jolivette, L. J.; Kirkpatrick, R. B.; Dul, E.; Khandekar, S. S.; Yi, T.; Jung, D. K.; Wright, L. L.; Smith, G. K.; Behm, D. J.; Bentley, R.; Doe, C. P.; Hu, E.; Lee, D. J. Med. Chem. 2007, 50, 6-9. (5) (a) Cheng, C. Y.; Mruk, D.; Silvestrini, B.; Bonanomi, M.; Wong, C.-H.; Siu, M. K. Y.; Lee, N. P. Y.; Lui, W.-Y.; Mo, M-Y. Contraception 2005, 72, 251-261. (b) Mruk, D. D.; Wong, C.-H.; Silvestrini, B.; Cheng, C. Y. Nature Med. 2006, 12, 1323-1328. (6) Benedini, F.; Bertolini, G.; Cereda, R.; Donà, G.; Gromo, G.; Levi, S.; Mizrahi, J.; Sala, A. J. Med. Chem. 1995, 38, 130-136. (7) Clark, R. D.; Caroon, J. M.; Kluge, A. F.; Repke, D. B.; Roszkowski, A. P.; Strosberg, A. M.; Baker, S.; Bitter, S. M.; Okada, M. D. J. Med. Chem. 1983, 26, 657-661. (8) Matsuoka, H.; Ohi, N.; Mihara, M.; Suzuki, H.; Miyamoto, K.; Maruyama, N.; Tsuji, K.; Kato, N.; Akimoto, T.; Takeda, Y.; Yano, K.; Kuroki, T.
Stereoselective Syntheses of 1,4-Dideoxy-1,4-imino-octitols and Novel Tetrahydroxyindolizidines
The Journal of Organic Chemistry, 2003
46), is reported. The synthesis is based on Knoevenagel homologation of the readily available enantiomerically pure pyrrolidin-carbaldehydes 13 and 37 followed by asymmetric dihydroxylation of the subsequent alkenyl pyrrolidines and cyclization of the corresponding imino-octitols. The new indolizidines and their precursors (imino-octitols 20, 25, 26) and indolizidinones 28a and 28b have been tested for inhibitory activities toward 26 glycosidases. The enzymatic inhibition of trans-7-hydroxy-D-(-)-swainsonine (44) toward R-mannosidases is similar to that described for trans-7-hydroxy-L-(+)-swainsonine (11b) toward naringinase (R-L-rhamnosidase from Penicillium decumbens).
Elsevier, 2005
The reactive 1:1 intermediate produced in the reaction between alkyl or aryl isocyanides and dialkyl acetylenedicarboxylates was trapped by 4,5-diphenyl-1,3-dihydro-2H-imidazol-2-one to yield highly functionalized 2,3-diphenyl-5H-imidazo[2,1-b][1,3]oxazine derivatives in fairly good yields. q
HETEROCYCLES, 1998
Iodine oxidation of 2-alkyl-1,4-naphthoquinones (1) in the presence of substituted pyridines (2) afforded naphtho[2,3-blindolizine-6,ll-dione derivatives (3). Other oxidant systems (MnO,/I' or Fe(ClO,),)iI,) can be used and 2alkylbenmquinones reacted in lower yield. Iodination of 3 by I, and dibenmyl peroxide occurred selectively at position 12. The a$-unsaturated carbonyl system of quinones has provided several examples of Michael addition of neutral and charged nucleophiles. The main preparative use of these processes is that the quinol addition products can be oxidized back to quinones; the overall process W i g a direct substitution of the quinone by an electronegative atoms.' Under acidic oxidative conditions, the additiodoxidation sequence can be easily performed in synthetically useful yields until poly~ubstitution.'~ The use of basic oxidative conditions was less extensively investigated, but it should provide access to a wide variety of symmetrical and unsymmetrical polysubstituted quinones. In fact, the electronegative atoms firstly introduced in the oxidation step can undergo fast nucleophilic substitution by appropriate bases present in the reaction medium. We have recently reported an example of this strategy in the four electron oxidation of 1,4naphthoquinone by wet iodine or hydrogen peroxide in the presence of substituted pyridines to give 2oxy-3-(pyridinium-1'-yl)-1,4-naphthoquin (NIO sub~titution).~ However, under these conditions, aliphatic a$-unsaturated carbonyl compounds gave vinylic a-substitution through a nucleophilic additiodelectrophilic capture/elimination pathway." This different behavior prompted us to investigate the reactivity of 2-akylquinones under basic oxidative conditions. In this paper, we report that 2-a&l-1,4