Synthesis of homologs of 2-aminoethylphosphonic acid

Conclusions Some homologs of 2-aminoethylphosphonic acid were synthesized by the addition of dialkyl phosphites to nitroolefins and the subsequent reduction of the thus obtained esters of 2-nitroethylphosphonic acid to the amino esters. Hydrolysis of the latter gave the free acids.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1382–1385, June, 1973.     

Synthesis of phosphonodipeptide conjugates of ursolic acid and their homologs

To prepare novel derivatives of naturally bioactive 3β‐hydroxy‐urs‐12‐en‐28‐oic acid (ursolic acid) with unusual properties and broad spectrum of activities, a number of chemical reactions were conducted. First, a variety of α‐aminophosphonates were prepared by a series of reactions involving the three‐component Mannich type reaction as a key step. Second, an array of phosphonodipeptides and their homologs was synthesized through multistep reactions including condensation of phthalic anhydride with glycine or β‐alanine, chlorination of N‐blocked amino acids, coupling of acid chloride with α‐aminophosphonates and sequential hydrazinolysis. Finally, new classes of phosphonodipeptide conjugates of ursolic acid and their homologs were obtained by condensation of 3β‐acetoxy‐urs‐12‐en‐28‐oyl chloride with phosphonodipeptides and their homologs. © 2008 Wiley Periodicals, Inc. Heteroatom Chem 19:55–65, 2008; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20396     

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 trans-10-hydroxydec-2-enoic acid and related compounds

Syntheses of the two stereoisomeric 10-hydroxydec-2-enoic acids are described. The trans-isomer is identical with the main fatty acid isolated from royal jelly of honeybees.

Some compounds closely related to this trans-acid have also been prepared.

A convenient process for the preparation of 10-acetoxy-decanoic acid from castor oil has been developed.     

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 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 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 of 1,4-dihydro-2-methyl-4-oxo-3-quinolineglyoxylic acid and related compounds

The synthesis of 1,4-dihydro-1-methoxy or ethyl -2-methyl-4-oxo-3-quinolineglyoxylic acid derivatives are described. α-Acetoxy-1,4-dihydro-1-hydroxy-2-methyl-4-oxo-3-quinolineacetic acid esters ( 7a, 7a ), which are key intermediates, were prepared by catalytic hydrogenation of 2-acetoxy-3-acetyl-4-hydroxy-4-(2-nitrophenyl) crotonic acid lactone ( 6 ) in methanol or ethanol.     

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 C-nor-4,6-secocamptothecin and related compounds

C-nor-4,6-Secocamptothecin 2 , 4-ethyl-4-hydroxy-6-(2-quinolinyl)-1H-pyrano[3,4-c]pyridine-3,8(4H,7H)-dione, lacking the C-ring of camptothecin 1 , and its related compounds 3 and 4 were prepared from ethyl quinoline-2-carboxylate 7 . By an analogous reaction sequences, synthesis of 6-(2-pyridinyl)-1H-pyrano[3,4-c]-pyridine-3,8(4H7H)-dione derivatives 5 and 6 , which contain the B, D, and E ring of 1 , were achieved.     

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.