A new molecular mechanism of blue color development with protocyanin,a supramolecular pigment from cornflower,Centaurea cyanus

Protocyanin (1), a blue pigment of Centaurea cyanus, is composed of six molecules each of malonylflavone (2) and succinylcyanin (3), complexed with magnesium and ferric ions. The blue color of 1 is developed by an LMCT interaction between anthocyanin and ferric ion, rather than arising from the formation of a simple anhydrobase anion of the chromophore. The supramolecular structure of 1 was elucidated.     

Synthesis of trichotomine,a blue pigment obtained from clerodendron trichotomum thunb

Synthesis of trichotomine, a blue pigment obtained from $\text{clerodendron}$$\text{trichotomum}$ thunb.     

Synthesis of trichotomine,a blue pigment obtained from clerodendron trichotomum thunb

The synthesis of trichotomine 1 possessing a new and novel chromophore has been achieved based on its biogenesis. Starting from l-tryptophan methyl ester and succinic anhydride, trichotomine 1 was synthesized by the following sequence: 7→8→9→6→2→1.     

Thermal dissociation of supramolecular complexes on the basis of 18-crown-6 and amino acids

The possibility of isolation of crystalline supramolecular complexes of 18-crown-6 with glycine, L-alanine, L-valine, L-leucine, L-phenylalanine, L-proline, L-hystidine, and L-threonine from aqueous solutions was studied. Comparative analysis of thermal decomposition of the complexes and their individual components and mechanical mixture was studied by means of thermogravimetry, differential thermal analysis, and differential scanning calorimetry. Crystaline complexes of 18-crown-6 with glycine, L-alanine, and L-hystidine were isolated and shown to be stable up to 140°C, which was additionally confirmed by IR spectroscopy.Translated from Zhurnal Obshchei Khimii, Vol. 74, No. 8, 2004, pp. 1313–1317.Original Russian Text Copyright © 2004 by Terekhova, Kulikov, Barannikov.This revised version was published online in April 2005 with a corrected cover date.     

Investigations towards the synthesis of xylindein,a blue-green pigment from the fungus Chlorociboria aeruginosa

An approach towards the synthesis of the fungal pigment xylindein 1 is described. Synthesis of the pyranonaphthoquinone corresponding to one half of the xylindein framework is achieved over 11 steps from 1,2-epoxypentane, utilizing multiple Diels–Alder cycloaddition processes. Methods for self-coupling of dihydroxynaphthoquinones to give extended quinones are explored.     

Total synthesis of the 6-silasteroid ring system

The total synthesis of the first¹ silasteroid ring system is described. A bidirectional construction was employed, starting from precursors of rings A and D. Metal-organic substitutions on dimethyldichlorosilane gave the allyl-m-methoxyphenyl derivative 2, as elements of rings AB. Hydroboration-oxidations led to the arylsilylpropionic acid 5. Activation and cyclization gave the key intermediate, 4,4 - dimethyl - 4 - sila - 6 - methoxy - 1 - tetralone, 7. Attachment of ring D and closure of ring C followed the Torgov-Smith outline, but required important differences in implementation, to give D,L-6, 6 - dimethyl - 6 - sila - 3 - methoxy - estra - 1,3,5(10),8,14 - pentaene - 17 - one, 11. Extensive physical data are presented.     

Total synthesis of munchiwarin, a triprenylated chalcone from Crotalaria medicagenia

An efficient method is developed for the synthesis of the modified triprenylated chalcone, munchiwarin (1), isolated from the roots of Crotalaria medicagenia. The synthesis of 1 utilizes a Claisen-Schmidt condensation between 2,4-dihydroxy-3,5-C-diprenyl acetophenone and 4-methoxy benzaldehyde in the presence of Ba(OH)2 to yield the unusual chalcone 5 that contains a nine-membered ether ring. Further prenylation of 5 with 1-bromo-3-methylbut-2-ene and its subsequent demethylation with BBr3 gave munchiwarin (1).     

Total synthesis of mycothiazole, a polyketide heterocycle from marine sponges

Mycothiazole isolated from marine sponges has been efficiently synthesized in a convergent manner. The key reactions involve the thiazole synthesis by dehydrogenation of the thiazolidine with chemical manganese dioxide (CMD), the Stille coupling, and the Nagao asymmetric acetate aldol reaction using the chiral 1,3-thiazolidine-2-thione. This synthesis clearly established the absolute configuration of natural mycothiazole to be (R).     

Total synthesis of 5, 6, 7, 8-tetrahydroquinolines and quinolines

The condensation of 2-ethoxy-2,3-tetramethylene-3,4-dihydro-l,2-pyran with acetal and ethyl orthoformate was studied. The condensation products react with ammonia on -aluminum oxide to form the corresponding tetrahydroquinolines; a mixture of tetrahydroquinolines and quinolines is formed from these condensation products on platinized --aluminum oxide.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1533–1534, November, 1971     

Total synthesis of milbemycins: a synthesis of (6R)-6-hydroxy-3,4-dihydromilbemycin E

Following studies using benzyloxymethyl isopropenyl ketone 5 and ethyl 3-(3-furyl)-3-oxopropanoate 6, Robinson reactions between aryloxymethyl isopropenyl ketones 19 and 5 and ethyl 3-(2-trimethylsilyl-3-furyl)-3-oxopropanoate 20 were found to be stereoselective giving cyclohexanones 21 and 41, in which the 3-(arylmethoxy) substituents were cis to the 2-hydroxyl groups, as the major products. After reduction and protection of ketone 21, selective PMB-deprotection, oxidation and stereoselective reduction inverted the configuration at C3 to give the diol 30. Protection of the secondary 3-hydroxyl group followed by modification of the protected 4-alcohol then gave the hydroxybutenolides 36 and 37 after oxidation of the silylated furan using singlet oxygen. The 3-benzyloxycyclohexanone 41 was also converted into the hydroxybutenolide 37 via the (2-trimethylsilylethoxy)methyl (SEM) ether 35. The Wittig reaction between the ylid generated from 2-methylpropyl(triphenyl)phosphonium salt and hydroxybutenolide 36 gave predominantly the (2Z,4Z)-dienyl acid 38 which was taken through to the butenolide 40. Similarly, the racemic hydroxybutenolide 37 was condensed with the racemic ylid derived from phosphonium salt 53 to give, after SEM-deprotection and 5-membered lactone formation, a mixture of the (9Z,2'Z)-dienyl lactones 58 and 59 containing ca. 10% of the corresponding (9Z,2'E)-isomers 60 and 61. (2'Z)/(2'E)-Isomerisation of the dienes 58 and 59 using iodine followed by deprotection gave a mixture of the seco-acids 62 and 63. Selective macrocyclisation of the seco-acid 62 in which the relative configuration of the C1-C7 and C17-C19 fragments (milbemycin numbering) corresponded to that present in the natural milbemycins, gave the beta-milbemycin analogue 65 after butenolide reduction. The hydroxybutenolide 37 was also condensed with the ylid derived from the phosphonium salt 1 and the product taken through to (6R)-6-hydroxy-3,4-dihydromilbemycin E 77. Preliminary attempts to convert the beta-milbemycin analogues 65 and 77 into tetrahydrofurans corresponding to analogues of alpha-milbemycins by treatment with toluene p-sulfonyl chloride under basic conditions gave the primary allylic chlorides 78 and 79.     

Total synthesis of spiruchostatin B, a potent histone deacetylase inhibitor, from a microorganism

The first total synthesis of spiruchostatin B, a potent histone deacetylase inhibitor, was achieved in a convergent manner; the synthesis established stereochemistry at the C5' position.     

Synthetic studies on the molybdenum cofactor: Total synthesis of pterindithiolenes by direct dithiolene formation from suitable pterin alkynes

A novel, efficient total synthesis of a series of pterindithiolenes (15, 16, 17 and 18) [(5,6-dihydro-[1,4]dithiin or 6,7-dihydro-5H-[1,4]dithiepin systems respectively for six and seven membered dithiolenes] has been reported. The six membered quinoxaline thioketal 9 and seven membered quinoxaline dithiolene 11 have also been synthesized from quinoxaline acetylenic alcohol 5 and the corresponding acetylenic ketone 10 respectively. The synthesis of five membered pterin thioketals 12 and 13 along with the conversion of 13 to the dithiolene 14 by the reaction with NBS is also reported.     

Total synthesis of halipeptin A, a potent anti-inflammatory cyclodepsipeptide from a marine sponge

Total synthesis of halipeptin A, a potent anti-inflammatory cyclodepsipeptide, was achieved through proline-catalyzed asymmetric α-oxidation, diastereoselective aldol reaction, silver cyanide-mediated esterification, and macrolactamization.     

Total synthesis of a cytotoxic acetogenin,pyranicin

[structure: see text] The first total synthesis of a new cytotoxic acetogenin, pyranicin (1), is described. SmI(2)-induced reductive cyclization of beta-alkoxy acrylate 4 proceeded stereoselectively to give 16,20-syn-19,20-trans-THP derivative 14, which was efficiently transformed into the 19,20-cis-THP derivative 18 through Mitsunobu lactonization. Wittig reaction of the phosphonium salt 2 obtained therefrom with butenolide 3 at -78 degrees C followed by reduction and deprotection afforded 1 in good overall yield.     

Total synthesis of a marine alkaloid from the tunicate Dendrodoa grossularia

A short synthesis of an indole marine alkaloid (1) from the tunicate Dendrodoa grossularia is described. The key step in the synthesis involves a novel twist on an underutilized oxazole rearrangement, which produces the quaternary stereocenter in the molecule.     

Total synthesis of 6-deoxyclitoriacetal isolated from Stemona collinsae Craib.

A total synthesis of the rotenoid, 6-deoxyclitoriacetal, a cytotoxic natural product, was successfully achieved by using platinum-catalysed hydroarylation, Sharpless asymmetric dihydroxylation, regioselective IBX diol oxidation and stereoselective intramolecular keto-aldehyde pinacol coupling as the key steps.     

Total synthesis of rutamycin B, a macrolide antibiotic from Streptomyces aureofaciens.

Rutamycin B (2) was synthesized from three principal subunits, spiroketal 75, keto aldehyde 83, and aldehyde 108. First, triol 62 was assembled by Julia coupling of sulfone 56 with aldehyde 58 followed by an acid-catalyzed spiroketalization. The three hydroxyl functions of 62 were successfully differentiated, leading to phosphonate 75. The latter was condensed in a Wadsworth-Emmons reaction with 83, prepared in six steps from (R)-aldehyde 76, to give 92. Coupling of the titanium enolate of 92 with 108 afforded Felkin product 109 with high stereoselectivity in a process that is critically dependent on the presence of the p-methoxybenzyl ether in the aldehyde. Transformation of 109 via aldehyde 116 to vinylboronate 122 was followed by macrocyclization under Suzuki conditions to yield 123. Exhaustive desilylation of the latter yielded rutamycin B.     

Total synthesis of alboatrin, a phytotoxic metabolite from Verticillium alboatrum

A synthesis of the phytotoxic metabolite alboatrin 1 is described. An intramolecular ketene-olefin cycloaddition followed by an oxidative ring enlargement was employed to generate the tricyclic ring system.