Reaction des glycosyl isonitriles avec les amines et les alcools

Marmet, D.; Boullanger, Paul; Descotes, G.

doi:10.1139/v81-057

Cited by 11 publications

(2 citation statements)

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“…Isocyanide 2a was further characterized chemically by its reaction with cinnamic acid. As expected, 14 it furnished 3-[formyl(3-phenylprop-2-enoyl)amino]isobenzofuran-1(3H)one (5) (Scheme 4).…”

Section: Scheme 1 Proposed Route For the Synthesis Of 3-isocyanoisobesupporting

confidence: 70%

Synthesis, Rearrangement, and Hauser Annulation of 3-Isocyanophthalides

2015

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7 examples 23-56% yields O O NC X O O CN X Tf 2 O 2,6-lutidine 0 °C r.t. 12 examples 8 examples 62-80% yields base CO 2 Me CO 2 Me OH OH R RAbstract 3-Isocyanoisobenzofuran-1(3H)-ones (phthalides) were prepared in two steps from the corresponding phthalaldehydic acids. The 3-isocyanoisobenzofuran-1(3H)-ones are readily rearranged to the corresponding 3-cyanoisobenzofuran-1(3H)-ones using triflic anhydride and 2,6-lutidine, thus enabling the synthesis of 3-cyanoisobenzofuran-1(3H)-ones without using toxic cyanide. Furthermore their annulation with Michael acceptors results in direct formation of 1,4-naphthoquinols/1,4-naphthoquinones in moderate yields.

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Section: Scheme 1 Proposed Route For the Synthesis Of 3-isocyanoisobesupporting

confidence: 70%

Synthesis, Rearrangement, and Hauser Annulation of 3-Isocyanophthalides

2015

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“…Eine ahnliche Konformation findet sich im kristallinen I -Desoxy-2,3 : 5,6-di-O-isopropyliden-1-nitro-a-D-mannofuranosylbromid [I] (Diederwinkel 8,l"). In den a-Nitroathern 20 [23], 21 [24] und 22 [25] betragen die entsprechenden Diederwinkel 21,5",10,[3][4][5][6][7][8][9][10][11][12][13]8 vicinalen cis-standigen Protonen (vgl. Tub.…”

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Desoxy‐nitrozucker. 3. Mitteilung. Synthese von Ketosen durch Kettenverlängerung von 1‐Desoxy‐1‐nitro‐aldosen. Nucleophile Additionen und Solvolyse von Nitroaethern

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Prewo

et al. 1982

Helvetica Chimica Acta

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A method for the preparation of chain elongated uloses based upon the basecatalyzed addition of 1-deoxy-1-nitroaldoses to aldehydes and Michael acceptors and subsequent solvolytic replacement of the nitro group by a hydroxy group is described. Thus, addition of 1, 3 and 9 to formaldehyde. followed by solvolysis gave the chain elongated ulose derivatives 2, 8 and 10 (63-76%), respectively. The configuration at the anomeric center of the addition products was deduced from 13C-NMR. spectra and mutarotation. In the case of 3, the primary addition products 4 and 6 were isolated and acetylated to 5 and 7. The nitro derivatives 4-7 do not follow Hudson's rule of isorotation. Addition of 1 to benzaldehyde (44%) and to nonanal (74%) proceded with a small degree of diastereoselectivity to give 15a/15b, and 11/12, respectively. The configuration of the secondary hydroxyl group of 12 was determined by correlation with methyl 2-hydroxydecanoate (14). Addition of 1 to the galuctoaldehyde 16 gave a single compound 17 (78%). The structure of this dodecosulose was determined by X-ray crystallography. Solvolysis of the acetylation product 18 in formamide gave the hemiacetal 19 (69%). Michael addition of 1 to acrylonitrile, methyl vinyl ketone and cyclohexenone under solvolytic conditions gave the hemiacetals 27, 30 and 31a,b (49%, 71% and 76%, respectively). Under non-solvolytic conditions (Bu4NF), 1 reacted with acrylonitrile, and crotononitrile to give the anomeric nitro ethers 23 and 24 (67%) and 25 and 26 (84%), respectively. Similarly, 3 added to acrylonitrile to give 28 and 29 (55%, 4: 1). This reaction appears to proceed under kinetic control. Addition of 1 to ethyl propiolate and solvolysis yielded the unsaturated spirolactone 32 (50%) and the ') 2.Mitteilung: [I]. 2, Korrespondenzautor. 00 18-0 19)3/82/7/22S i -22$01 .00/0 0 1982 Schweizerische Chemisehe Gesellschaft 2252 HELVPTICA CHIMICA ACTA -Vol. 65, F a x . 7 (1982) -Nr. 220 hemiacetal33 (17%). Hydrogenation of 32 gave the saturated spirolactone 34 (100%) which was also obtained from 1 and methyl acrylate (63%). Addition of 1 to dimethylmaleate gave the unsaturated ester 35 (48%). 1. Einleitung. -Hohere Zucker sind ausgehend von Aldosen durch Verlangerung der C-Kette am anomeren Zentrum oder am Kettenende zuganglich [2] [3]. Zur Kettenverlangerung vom anomeren Zentrum aus werden beinahe ausschliesslich (gegebenenfalls umgepolte) Carbanionen verwendet. Bei den klassischen Methoden sind dies Aquivalente von Formyl-anionen, wie Cyanid [2], Nitromethananion (21 und Diazomethan [2]. Methoden zur Umpolung der Reaktivitat am anomeren Zentrum sind zur Erweiterung der synthetischen Moglichkeiten ebenfalls erwunscht, mussen jedoch a priori (ausser im Fall von 2-Desoxyzuckern) eine P-Eliminierung vermeiden. Dies ist Paulsen mit der Verwendung von offenkettigen, doppelt deprotonierten, von Monosacchariden abgeleiteten 2-Hydroxydithianen erstmals gelungen [4], wahrend die cyclischen, geschutzten 1 -Desoxy-1 -isocyanaldosen von Descotes et al. [ S ] sich zu diesem Zweck nicht eig...

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