Abstract:
:Using the unique character of the chiral Pd complexes 1 and 2, highly efficient catalytic asymmetric reactions have been developed. In contrast to conventional Pd(0)-catalyzed reactions, these complexes function as an acid-base catalyst. Thus active methine and methylene compounds were activated to form chiral palladium enolates, which underwent enantioselective carbon-carbon bond-forming reactions such as Michael reaction and Mannich-type reaction with up to 99% ee. Interestingly, these palladium enolates acted cooperatively with a strong protic acid, formed concomitantly during the formation of the enolates to activate electrophiles, thereby promoting the C-C bond-forming reaction. This palladium enolate chemistry was also applicable to electrophilic enantioselective fluorination reactions, and various carbonyl compounds including beta-ketoesters, beta-ketophosphonates, tert-butoxycarbonyl lactone/lactams, cyanoesters, and oxindole derivatives could be fluorinated in a highly enantioselective manner (up to 99% ee). Using this method, the catalytic enantioselective synthesis of BMS-204352, a promising anti-stroke agent, was achieved. In addition, the direct enantioselective conjugate addition of aromatic and aliphatic amines to alpha,beta-unsaturated carbonyl compound was successfully demonstrated. In this reaction, combined use of the Pd complex 2 having basic character and the amine salt was the key to success, allowing controlled generation of the nucleophilic free amine. This aza-Michael reaction was successfully applied to asymmetric synthesis of the CETP inhibitor torcetrapib.
journal_name
Chem Pharm Bull (Tokyo)journal_title
Chemical & pharmaceutical bulletinauthors
Hamashima Ydoi
10.1248/cpb.54.1351subject
Has Abstractpub_date
2006-10-01 00:00:00pages
1351-64issue
10eissn
0009-2363issn
1347-5223pii
JST.JSTAGE/cpb/54.1351journal_volume
54pub_type
杂志文章,评审abstract::Four new dibenzocyclooctadiene lignan glucosides, schisandrosides A-D (1-4), as well as two known rare nortriterpenoids, micrandilactone C (5) and propindilactone Q (6), were isolated from the roots of Schisandra chinensis BAILLON (Schisandraceae). The structure of compounds 1-4 were elucidated by physical and spectro...
journal_title:Chemical & pharmaceutical bulletin
pub_type: 杂志文章
doi:10.1248/cpb.c15-00400
更新日期:2015-01-01 00:00:00
abstract::Study was carried out to develop two simple, fast, accurate and sensitive spectrophotometric methods (A and B) for the determination of citalopram hydrobromide in commercial tablet formulations. In method A, UV spectrophotometer determined the contents of citalopram hydrobromide in tablets at 240 nm in methanol solven...
journal_title:Chemical & pharmaceutical bulletin
pub_type: 杂志文章
doi:10.1248/cpb.54.432
更新日期:2006-04-01 00:00:00
abstract::New antitumor alkylglycerophospholipids, in which primarily the phosphocholine moiety of the platelet activating factor (PAF) molecule was modified, were synthesized from 1-alkyl-2-substituted glycerols by introducing polar head phosphoryl groups having methylene bridges of various lengths (from 2 to 14 carbons). They...
journal_title:Chemical & pharmaceutical bulletin
pub_type: 杂志文章
doi:10.1248/cpb.37.1249
更新日期:1989-05-01 00:00:00
abstract::Electron spin resonance studies showed that addition of rat liver microsomes to the reaction system of alloxan with reduced nicotinamide adenine dinucleotide phosphate (NADPH) resulted in a marked increase in the generation of alloxan radicals (AH.), whereas heat-denatured microsomes were without such effect. Oxidatio...
journal_title:Chemical & pharmaceutical bulletin
pub_type: 杂志文章
doi:10.1248/cpb.40.432
更新日期:1992-02-01 00:00:00
abstract::Absorption spectra of polycrystalline L-, D-, and DL-tartaric acid have been measured by terahertz time domain spectroscopy (THz-TDS). Different absorption bands are observed for DL-tartaric acid and its enantiomers (L- and D-tartaric acid). This result shows that the THz-TDS can be used for distinguishing between DL-...
journal_title:Chemical & pharmaceutical bulletin
pub_type: 杂志文章
doi:10.1248/cpb.56.305
更新日期:2008-03-01 00:00:00
abstract::We developed a rapid and efficient analytical technique for cyclosporine A using HPLC on a column packed with 2-µm nonporous octadecylsilyl silica particles. Under optimized conditions, cyclosporine A was separated with high resolution from other cyclic peptides within 3 min, because the mass transfer resistance in th...
journal_title:Chemical & pharmaceutical bulletin
pub_type: 杂志文章
doi:10.1248/cpb.c18-00279
更新日期:2018-01-01 00:00:00
abstract::An uncommon, previously unreported p-quinone-lignan compound called justicidone (4-(1,3-benzodioxol-5-yl)-6-methoxynaphtho[2,3-c]furan-1,5,8(3H)-trione) (2), along with the known savinin (1) were isolated from Justicia hyssopifolia (Acanthaceae). Their structures were determined by spectroscopic methods. ...
journal_title:Chemical & pharmaceutical bulletin
pub_type: 杂志文章
doi:10.1248/cpb.52.130
更新日期:2004-01-01 00:00:00
abstract::(+)-4(5)-[(2R,5R)-5-aminomethyltetrahydrofuran-2-yl]imidazole [(+)-1, imifuramine] and its 2R,5S-stereoisomer (+)-2 were expected as base compounds to develop selective human histamine H4-receptor ligands. The improved synthesis of (+)-1 was done via cyclization of a diazafulvene intermediate generated by Bu3P/N,N,N',...
journal_title:Chemical & pharmaceutical bulletin
pub_type: 杂志文章
doi:10.1248/cpb.51.832
更新日期:2003-07-01 00:00:00
abstract::A new monomethylated ganglioside, DSG-A (3), was obtained, together with four known gangliosides, compounds (1, 2, 4, 5), from the lipid fraction of the chloroform/methanol extract of the ovary of the sea urchin Diadema setosum. The structures of the new ganglioside was determined on the basis of chemical and spectros...
journal_title:Chemical & pharmaceutical bulletin
pub_type: 杂志文章
doi:10.1248/cpb.56.734
更新日期:2008-05-01 00:00:00
abstract::A new extension of the Hildebrand solubility approach which describes drug solubility in solvent mixtures showing multiple solubility peaks, the chameleonic effect, is proposed. The experimental solubilities of oxolinic acid were measured at 25 degrees C in solvent mixtures of ethanol-water and ethanol-ethyl acetate. ...
journal_title:Chemical & pharmaceutical bulletin
pub_type: 杂志文章
doi:10.1248/cpb.48.175
更新日期:2000-02-01 00:00:00
abstract::A series of about fifty novel 5-arylfuro[2,3-d]pyrimidine derivatives were synthesized as potential inhibitors of dihydrofolate reductase (DHFR) arising from different species. Weak enzyme inhibition was observed for most of the compounds, with only a few reaching IC50 values less than 30 microM. With regards to antib...
journal_title:Chemical & pharmaceutical bulletin
pub_type: 杂志文章
doi:10.1248/cpb.47.156
更新日期:1999-02-01 00:00:00
abstract::Tetrasubstituted (Z)-alkenes were readily prepared through the Horner-Wadsworth-Emmons reactions of methyl 2-[bis(2,2,2-trifluoroethyl)phosphono]propionate with aryl alkyl ketones by employing Sn(OSO(2)CF(3))(2) and N-ethylpiperidine. ...
journal_title:Chemical & pharmaceutical bulletin
pub_type: 杂志文章
doi:10.1248/cpb.50.1300
更新日期:2002-09-01 00:00:00
abstract::From Puerariae Radix, the root of Pueraria lobata (Leguminosae), six new oleanene-type triterpene glycosides, called kudzusaponins A1 (1), A2 (2), Ar (3), SA4 (5), and SB1 (6) were isolated together with kudzusaponin A3 (7), soyasaponins SA3 (8), and I (9). The structures of 1-6 were determined to be 3-O-alpha-L-rhamn...
journal_title:Chemical & pharmaceutical bulletin
pub_type: 杂志文章
doi:10.1248/cpb.45.362
更新日期:1997-02-01 00:00:00
abstract::Amodiaquine (AQ) is an antimalarial which is effective against chloroquino-resistant strains of Plasmodium falciparum but whose clinical use is severely restricted because of associated hepatotoxicity and agranulocytosis. "One-pot" synthesis of formamidines likely to be transformed into AQ derivatives is reported. Com...
journal_title:Chemical & pharmaceutical bulletin
pub_type: 杂志文章
doi:10.1248/cpb.49.933
更新日期:2001-08-01 00:00:00
abstract::Sodium nitroprusside (SNP) releases nitric oxide (NO), a powerful vasodilator, and thus widely used in intensive care unit for treating hypertension emergency. However, cardiac toxicity after SNP administration is a clinical problem. For finding a natural compound that suppressing SNP-induced cardiac toxicity, we test...
journal_title:Chemical & pharmaceutical bulletin
pub_type: 杂志文章
doi:10.1248/cpb.c13-00995
更新日期:2014-01-01 00:00:00
abstract::Adriamycin linked to oxidized dextran (ADM-OXD) via Schiff's base formation was compared with free adriamycin with regard to antitumor activity, acute toxicity and plasma pharmacokinetics in rats following i.v. administration. ADM-OXD showed higher activity against Walker carcinosarcoma 256 than free adriamycin. On th...
journal_title:Chemical & pharmaceutical bulletin
pub_type: 杂志文章
doi:10.1248/cpb.37.1639
更新日期:1989-06-01 00:00:00
abstract::The combination of electrolysis and the Fe(III)(PA)3/O2/CH3CN system was investigated for allylic hydroxylation of octahydronaphthalene derivatives. Substrates with a bridgehead double bond gave the allylic alcohol with alpha-preference, while non-bridgehead olefin did not react smoothly. This system is a useful tool ...
journal_title:Chemical & pharmaceutical bulletin
pub_type: 杂志文章
doi:10.1248/cpb.53.248
更新日期:2005-02-01 00:00:00
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journal_title:Chemical & pharmaceutical bulletin
pub_type: 杂志文章
doi:10.1248/cpb.c17-00721
更新日期:2018-01-01 00:00:00
abstract::Eight new myriocin analogs, 2-epi-myriocin, Z-14-deoxomyriocin, and nor-deoxomyriocins, and a known myriocin derivative, 14-deoxomyriocin, were synthesized from 2-deoxy-D-glucose via common intermediates in previous myriocin and Z-myriocin syntheses. The immunosuppressive activities of new myriocin analogs and Z-myrio...
journal_title:Chemical & pharmaceutical bulletin
pub_type: 杂志文章
doi:10.1248/cpb.42.2662
更新日期:1994-12-01 00:00:00
abstract::The synthesis and biological evaluation of [2-Valine-A] insulin ([Val2-A]insulin) is reported. In this insulin, the isoleucine residue in position A2, invariant in the majority of mammalian insulins, is substituted by valine. The same substitution, along with four others, occurs naturally in the insulin produced by th...
journal_title:Chemical & pharmaceutical bulletin
pub_type: 杂志文章
doi:10.1248/cpb.37.670
更新日期:1989-03-01 00:00:00
abstract::Particles of poorly water-soluble drugs were prepared to develop a dry powder inhaler (DPI). Spray freeze-drying (SFD) technique using a four-fluid nozzle (4N), which has been developed by authors, was applied in this research. Ciclosporin and mannitol were used as a poorly water-soluble model drug and a dissolution-e...
journal_title:Chemical & pharmaceutical bulletin
pub_type: 杂志文章
doi:10.1248/cpb.c12-00208
更新日期:2012-01-01 00:00:00
abstract::From the MeOH extract of the aerial part of Vietnamese Orthosiphon stamineus, five new isopimarane-type diterpenes [orthosiphols F-J (1-5)] and two new diterpenes [staminols A (6) and B (7)] with a novel carbon-framework, to which we proposed the name "staminane", and three new highly-oxygenated staminane-type diterpe...
journal_title:Chemical & pharmaceutical bulletin
pub_type: 杂志文章
doi:10.1248/cpb.48.1711
更新日期:2000-11-01 00:00:00
abstract::Repeated silica gel and octadecyl silica gel (ODS) column chromatography of the aerial parts of Artemisia princeps PAMPANINI (Sajabalssuk) led to the isolation of a new sesquiterpenoid, 3-((S)-2-methylbutyryloxy)-costu-1(10),4(5)-dien-12,6 alpha-olide (2), along with two previously reported sesquiterpenoids: 8 alpha-a...
journal_title:Chemical & pharmaceutical bulletin
pub_type: 杂志文章
doi:10.1248/cpb.56.1168
更新日期:2008-08-01 00:00:00
abstract::Our aim is to test the characteristics and expression activity in brain capillary endothelial cells (BCECs) of DNA-loaded nanoparticles before and after the modification with Antennapedia peptide (Antp). Chitosan (CH), polyethylenimine (PEI) and polyamidoamine (PAMAM) were chosen to prepare the nanoparticles; Lipofect...
journal_title:Chemical & pharmaceutical bulletin
pub_type: 杂志文章
doi:10.1248/cpb.54.1254
更新日期:2006-09-01 00:00:00
abstract::Three new hydronaphthalenone derivatives (1-3) and one new dihydroramulosin derivative (4), were isolated from the endophytic fungus PSU-N24 together with eight known compounds. Their structures were elucidated by spectroscopic methods. Griseofulvin (9) displayed strong antifungal activity against Microsporum gypseum ...
journal_title:Chemical & pharmaceutical bulletin
pub_type: 杂志文章
doi:10.1248/cpb.56.1687
更新日期:2008-12-01 00:00:00
abstract::Arginine-vasopressin (AVP) was acylated with various acyl azides (2a-j) in pH 9.1 buffer to give AVP derivatives (11a-j) modified at the tyrosine side chain with a carbohydrate via a spacer arm. Glycoconjugates of AVP modified at the N-terminal amide (12a-e) were also synthesized from AVP and carboxylic acids (3a-e) u...
journal_title:Chemical & pharmaceutical bulletin
pub_type: 杂志文章
doi:10.1248/cpb.46.1530
更新日期:1998-10-01 00:00:00
abstract::Six novel acyclic sulfides, named garlicnins L-1-L-4 (1-4), E (5), and F (6), were isolated from the acetone extracts, with the ability to suppress M2 macrophage activation, of the bulbs of garlic (Allium sativum L.), and their chemical structures were characterized. ...
journal_title:Chemical & pharmaceutical bulletin
pub_type: 杂志文章
doi:10.1248/cpb.c14-00003
更新日期:2014-01-01 00:00:00
abstract::Four new diterpenes, 3-oxosaprorthoquinone (1), 3-oxomicrostegiol (2), 3-oxoisotaxodione (3), and taiwaninal (4), together with two known compounds, 3-oxosapriparaquinone (5) and 6-dehydrohinokiol (6), were isolated from the roots of Taiwania cryptomerioides. The structures of 1-4 were principle elucidated based on sp...
journal_title:Chemical & pharmaceutical bulletin
pub_type: 杂志文章
doi:10.1248/cpb.53.11
更新日期:2005-01-01 00:00:00
abstract::Synthesis and pharmacological evaluation of novel thienopyridazinones and related compounds are described. A thiophene ring was found to be able to replace the benzene ring of a phthalazinone without loss of biological activities. This observation supports our hypothesis that the benzene ring plays an important role i...
journal_title:Chemical & pharmaceutical bulletin
pub_type: 杂志文章
doi:10.1248/cpb.43.236
更新日期:1995-02-01 00:00:00
abstract::Based on the result of X-ray crystallographic analysis of our peroxisome proliferator-activated receptor alpha and delta (PPARalpha/delta) co-agonist complexed with human PPAR ligand binding domain (LBD), we designed and synthesized an optically active fluorescent PPARalpha/delta co-agonist, which has a pyrene unit in...
journal_title:Chemical & pharmaceutical bulletin
pub_type: 杂志文章
doi:10.1248/cpb.56.1357
更新日期:2008-09-01 00:00:00