Synthesis of dl-guinesines and related compounds

Guinesines A, B and C were synthesized starting from 1,3-bis(benzylthio)-2-propanone and N-methyl-2,2-diethoxypyrrolidine.     

Synthesis of santonin related compounds

(±)-1-Nordesmotroposantonin ( 2 ), a thermolysis product of santonin, and its isomer, α-(1,2,3,4-tetrahydro-1,7-dihydroxy-α,6-dimethyl-2-naphthalene)acetic acid γ-lactone ( 3 ) were synthesized from 4-(4-methoxy-3-ethylphenyl)butanoic acid.     

Synthesis of shikalkin and certain related compounds

A successful total synthesis of a biologically active pigment from plants of the Boraginaceae family was carried out with naphthazarine as the starting material, and using the 1,4,5,8-tetramethoxynaphthalene, the corresponding 2-vinyl derivative and its epoxide or a cyclopropane adduct with diazoacetic ester at the key stages. In the course of developing the scheme of the synthesis of shikalkin, its three analogs were obtained, differing in the nature of the monoterpenoid side chain.For preliminary report, see [1].Pacific Ocean Institute of Bioorganic Chemistry, Far East Branch of the Russian Academy of Sciences, 690022 Vladivostok. N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, 117913 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 8, pp. 1901–1910, August, 1992.     

Synthesis of glycosyl phosphonates and related compounds

The synthesis of glycosylphosphonates, isopolar, nonisosteric analogues of glycosylphosphates, from halonitro ethers, glycosyl acetates, or glycosyl trichloroacetimidates is reviewed. A new approach to phosphonate analogues of myo-inositol trisphosphate ( 50 ) is described. Based on a hypothetical reaction mechanism for the formation of thioethers from a glyoxalase I inhibitor, an advanced intermediate 59 for the synthesis of diphosphonate–phosphate analogues of 50 is obtained by an addition–elimination–addition sequence from 54 . Finally, glucosylphosphines, characterized as the corresponding phosphine oxides 61 and 62 have been prepared from the glycosylidene diazirine 60 , a precursor of the tetra-O-benzylglucopyranosylidene carbene. The phosphine oxides 61 and 62 were also obtained by reaction of the glycosyl acetate 18 with methyl diphenylphosphinite.     

Synthesis of compounds related to muscarine

Conclusions A method was developed for obtaining muscarine analogs, and 2-methyl-5-(N-dimethylaminomethyl)-2,3-dihydro-3-furanone- the starting product for obtaining muscarine- was synthesized.     

Synthesis and studies of tris-indolobenzenes and related compounds

The unsymmetrical N,N,N-trimethyl tris-indolobenzene 3 has been synthesized by several routes, including cyclotrimerization of the O-acetate of indoxyl. This condensation involves a 3→2 rearrangement of the precursor formed in situ. Similar Wagner-Meerwein rearrangements were also prevalent in LAH reductions of some 3,3-diindolyl oxindoles.Treatment of the 3,3-diindolyl indolines with strong acid resulted in a cleavage yielding 3,3'-biindolyls.     

Synthesis of racemic brevioxime and related model compounds

The synthesis, in racemic form, of the insect juvenile hormone inhibitor brevioxime (1) is described, as well as exploratory studies that led to the related model compounds 14 and 15a. The route to 1 involves Ag(+)-mediated coupling of the amine derived from 20 with the beta-keto thioester 32. Acid treatment of the coupled product 33 led by acetal hydrolysis, cyclization, and desilylation to 34a,b, from which 1 was reached by oxidation and conversion into the oxime. In the synthesis of the amino component 20, a known, but unusual, reduction was used for converting a nitrile into an amine hydrochloride.     

Synthesis and antitumor activity of puupehedione and related compounds

The first enantiospecific synthesis of bioactive marine puupehedione (2) and related compounds from (−)-sclareol (11) is reported. The antitumor activity of these compounds was assayed and compared with that of the natural products.     

4，6－二硝基苯并氧化呋咱的合成

采用新的合成方法，以苦基氯为原料，经过叠氮化和脱氮环化反应，合成了苯并氧化呋咱化合物。对其结构作了理论分析和实验鉴定，认为该化合物具有杂芳结构。     

Synthesis of functionalized compounds containing pyridazine and related moieties

3‐Aminopyridazines 17 and 3‐hydrazinopyridazines 18 were used as building blocks for the preparation of various types of functionalized, pyridazine ring containing compounds. 3‐Aminopyridazines were employed in the synthesis of 3‐(6‐chloroimidazo[1,2‐b]pyridazin‐2‐yl)alanines 26, 27 and for the preparation of 3‐amino‐4H‐pyrimido[1,2‐b]pyridazin‐4‐ones 103 , intermediates in the ‘ring switching’ synthesis of alkyl 1‐pyridazin‐3‐yl‐1,2,3‐triazole‐4‐carboxylates 106 .On the other hand, hydrazinopyridazines 18 were employed in a two‐step preparation of 3‐functionalized 1,2,4‐triazolo[4,3‐b]pyridazines via condensation with functionalized aldehydes and their enamino analogs followed by oxidative cyclization of the intermediate hydrazones. In this manner, 1,2,4‐triazolo[4,3‐b]pyridazin‐3‐yl substituted alanines 29, 30 , polyols 33, 39–48 , C‐nucleosides 49, 50 , and terpenes 58, 62, 64–69 were prepared. In another general approach, 3‐hydrazinopyridazines 18 were treated with functionalized enaminones as 1,3‐dielectrophiles to give the 1‐(substituted pyridazin‐3‐yl)‐1H‐pyrazole derivatives containing an ester 72, 73, 75, 76 , alanine 79, 84, 85, 87 , 2‐phenylethylamine 97, 99 , and β‐amino alcohol functional element 98, 100 . In the reaction of 4‐oxohomoglutamate 82 with hydrazine hydrate and methyl hydrazine, chiral functionalized tetrahydropyridazinones 88a,b were obtained.     

Synthesis of biologically active acycloAZT derivatives and related compounds

The synthesis of optically active acyclic analogues of 3'-azido-3'-deoxythymidine, which lack only the 2'-CH2 of the sugar, is described. The synthesis of some nucleoside analogues that contain the N-acetyl-D-neuraminic acid moiety is also described.