2- -l-methoxycarbonyl

Ethoxycarbonyl-methyl)-l-(4-methoxycarbonyl-phenyl)- Elba, 1189 (Ar — Nf + Amin) 2H-l,2,3-Triazol 2-Phenyl-4-(1,2,3,4-tetrahydroxy-butyl)-IV/la, 896... 

Aus dem Natrium-Salz von 6-Nitro-lH-mdazol und 4-Brommethyl-benzoesaure-methylester wird in Aceton l-(4-Methoxycarbonyl-he.nzyl)-6-nitro-lH- (28% Schmp. 171-172,5°) sowie 2-(4-Methoxycarbonyl-benzyl)-6-nitro-2H-indazol (17% Schmp. 163-163,5°) erhalten699 4-Nitro-lH-indazol bildet mit Benzylchlorid bei 180° l-Benzyl-4-nitro-IH-5M (Schmp. 97°) und 2-Benzyl-4-nitro-2H-indazol533 (Schmp. 123-124°). 

In seeking a synthetic route to an antibiotic antitumor agent, the Thiele-Winter synthon, with 2,3-bis(methoxycarbonyl)-l,4-ben2oquinone [77220-15-6] (60), was used to introduce a required third oxygen linkage (57). A 67% yield of (61) was obtained. 

Unsymmetrical dienes in this synthesis are often capable of high regioselectivity (eqs. 4 and 5) (82). Reaction of (81) with 2-methoxycarbonyl-l,4-ben2oquinone [3958-79-0] yields 97% of (82) [80328-15-0]. Reaction of (81) with 2,3-dicyano-l,4-ben2oquinone [4622-04-2] yields 58% of (83) [80328-16-1]. 

Pyridinium iodide, l-ethyl-4-methoxycarbonyl-UV spectrum, 2, 127 Pyridinium iodide, 1-methyl-decomposition, 2, 300 Pyridinium iodide, 6-pterinylmethyl-synthesis, 3, 312... 

Pyridyl radicals, 4-methoxycarbonyl-l-methyldihydro-ES 2, 145 3-Pyridylmethanol as metabolite... 

The intramolecular cyclization of l-(4-bromobutyl)-3-methoxycarbonyl-l,4,5, 6-tetrahydropyridine (140) and l-(3-bromopropyl)-3-methoxycarbonyl-l,4,5,6-tetrahydropyridine (143) (89T5269) resulted in the synthesis of quinolizidine ring system 141 and indolizidine ring system 144 in 43% and 72% yields along with the reduced tetrahydropyridines 142 and 145 in 21% and 8% yields, respectively. All the cyclized products appeared to be (ran.s-fused indolizidines or quinolizidines. The (ran.s -fused simple indolizidines are known to be some 2.4 kcal mol more stable than the d.s-fused isomers (68TL6191). In the and-isomer the methoxycarbonyl substituent occupies an equatorial position. 

The synthetic utility of radical cyclization was used as the key step in a four-step synthesis of the natural product (d,0-epilupinine (134b, a quinolizidine alkaloid) (75CB1043) from methyl nicotinate (146). Thus, l-(4-bromobutyl)-3-methoxycarbonyl-l,4,5,6-tetrahydropyridine (140), obtained from methyl nicotinate (146), was cyclized to 141 (43%), which on reduction with LiAlH4 in THF provided 134b in 95% yield (89T5269). 

V,7V-dimethylaminopyridme provides l-(2-methoxycarbonyl)ethoxy- (40,69%) and l-(2-methoxycarbonyl-l-methyl)ethoxytryptamine (41, 72%), respectively (Scheme 4). The conjugate addition to mesityl oxide proceeds successfully as well, giving iVb-acetyl-1-(1, l-dimethyl-3-oxo)butoxytryptamine (42,49%), while the reaction with methyl 3-methylcrotonate affords 43 in a miserable yield (1.6%). Addition to acrolein results in failure, and 44 is not yet obtained. 

Cyclization of 1 -(9-fluorenylmethoxycarbonyl)-2-[(A-methoxycarbonyl-methyl)aminocarbonyl)piperidine and 2-(9-fluorenylmethoxycarbonyl) -3-[(A-methoxycarbonylmethyl)aminocarbonyl]-1,2,3,4-tetrahydroisoquino-lines on the action of piperidine in THF yielded 2-(l,4-dioxoperhydropyr-ido[ 1,2-fl]pyrazin-2-y 1)- and 2-( 1,4-dioxo-1,3,4,6,11,11 a-hexahydro-2//-pyr-azino[l,2-i]isoquinolin-2-yl)acetamides, respectively (99MIP11). 

Trost and co-workers have explored asymmetric transidon metal-catalyzed allylic alkyla-dons. Details on this subject have been well reviewed by Trost and others. With the use of asymmetric palladium-catalyzed desymmetrizadon of meso-2-ene-l,4-diols, cii -l,4-dibenzoy-loxy-2-cyclopentene can be converted to the enandometrically pure cii -4-rfirr-butoxycar-bamoyl-l-methoxycarbonyl-2-cyclopentene. The product is a usefid and general building block for synthesis of carbocyclic analogs of nucleosides as presented in Scheme 5.12. 

Kaeriyama et al. [10] reported on the Ni(0)-catalyzed coupling of 1,4-dibromo-2-methoxycarbonylbenzene to poly(2-methoxycarbonyl-l,4-phenylene) (4) as a soluble, processable precursor for parent PPP 1. The aromatic polyester-type PPP precursor 4 was then saponified to carboxylated PPP 5 and thermally decarboxy-latcd to 1 with CuO catalysts. However, due to the harsh reaction conditions in the final step, the reaction cannot be carried out satisfactorily in the solid state (film). 

The related serine derived (4S)-4-methoxycarbonyl-3-(l-oxopropyl)-2-thiono-l,3-oxazolidine 11, and the cysteine derived (4A)-4-methoxycarbonyl-3-(l-oxobntyl)-2-thiono-1,3-thiazolidine 13, also serve as efficient chiral auxiliaries in boron- and tin(II)-mediated aldol condensations98. Thus, conversion of 11 into the boron or tin enolate, followed by reaction with 2-methylpropanal affords predominantly one adduct. Subsequent methanolysis and chromatographic purification delivers the syu-methyl ester in 98% ee. 

N-(tert-Butoxycarbonyl)-P-4-(methoxycarbonyl)phenyl]alanine methyl ester L-Phenylalanine, N-[(l,l-dimethylethoxy)carbonyl]-4-(methoxycarbonyl)-, methyl ester (160168-19-4)... 

Athyl- 650, 652 1-Benzyl- 650, 652 l-Benzyl-3-aminocarbonyl- 650 1-Benzyl- -chlorid 593 l-Benzyl-4-methoxycarbonyl- -jodid 593... 

Only one procedure has been reported recently within this category. Thus 7-chloro-l-methyl-5-phenyl-2,3-dihydro-lH-benzodiazepin-2-one 4-oxide (437) with dimethyl acetylenedicarboxylate in methylene chloride at 20° C for 3 days gave a separable mixmre of the primary tricyclic adduct, dimethyl lO-chloro-6-oxo-llb-phenyl-5,6,7, 1 lb-tetrahydroisoxazolo[2,3-t/] [ l,4]benzodiazepine-1,2-dicarboxylate (438), and its rearrangement product, 6-chloro-4-(2-methoxalyl-2-methoxycarbonyl-l-phenylvinyl)-l-methyl-3,4-dihydro-2(lT0-quinoxalinone (439) each product afforded 6-chloro-l-methyl-2(l//)-quinoxalinone (440) on refluxing in ethanol (see also Section 1.7.13). However, the final quinoxaline (440) was best obtained in 75% yield) by simply heating the initial substrate (437) and dimethyl... 

Ethoxycarbonylmethyl-2(l//)-quinoxalinone (62) gave 3-methoxycarbonyl-methylene-l,4-dimethyl-3,4-dihydro-2(l/ )-quinoxalinone (63) (CH2N2,... 

Chloro-2-[l,4-dimethyl(thiosemicarbazido)]quinoxaline 4-oxide (250) with dimethyl acetylenedicarboxylate gave 6-chloro-2-[A-(5-methoxycarbonyl-methylene-3-methyl-4-oxo-2-thioxoimidazolidin-l-yl)-A-methylammo]quinoxa-line 4-oxide (251) (EtOH, reflux, 5 h 54%) a homolog likewise." ... 

CijHijNOj 83073-63-6) see Tilisolol hydrochloride l-methyl-2-[[4-(methoxycarbonyl)phenyl]methyl]-l,2-hy-drazinedicarboxylic acid bis(phenylmethyl) ester (CifiHjgNjOg) see Procarbazine 5-methyl-8-methoxycoumarin... 

We have recently investigated X-ray structure of 3-methoxycarbonyl-[l,4,2] diazaphospholo[4,5-a]pyridine as first example of molecular structure determination for [l,4,2]diazaphosphole ring [84], The ester substituent lies strictly in the molecular plane with carbonyl group in the trans orientation with the formal C=P bond. Endocyclic P-N and P-C bonds are averaged between respective single and double bond lengths. 

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