Enantioselective Hydrogenation over Chiral Cobalt Complexes with (+)-(1S,2S,5R)-Neomenthyldiphenylphosphine and (-)-(R,R)-2,2-Dimethyl-4,5-bis(diphenylphosphinomethyl)-1,3-dioxolane

The optical yield in enantioselective hydrogenation of methyl -acetamidocinnamate over mono- and diphosphine cobalt(II) complexes CoX₂L₂ [where X = Cl or CF₃SO₃, L = (+)-(1S,2S,5R)-neomenthyl-diphenylphosphine or L2' = (-)-(R,R)-2,2-dimethyl-4,5-bis(diphenylphosphinomethyl)-1,3-dioxolane], which are generated in situ, in the presence of sodium tetrahydridoborate increases with rise in the phosphine-to-metal ratio and hydrogen pressure. The maximal optical yields of (+)-(S)-N-acetylphenylalanine methyl ester attain 40% (CoX₂L₂) and 42% (CoX₂L₂').     

Synthetic Applications of 2-(1,3-Dithian-2-yl)indoles. 7. Synthesis of Aspidospermidine

A new method of synthesizing the alkaloid aspidospermidine (1), based on building ring E on the pyridocarbazole [ABCD] ring structure, is reported. The preparation of the pyridocarbazole framework of Aspidosperma alkaloids is a new three-step synthetic application of 2-(1,3-dithian-2-yl)indoles. A tandem conjugate addition-alkylation reaction starting from indolyldithiane (4), 3-methylenelactam 6, and EtI yields the adduct 17. Treatment of lactam 17 with DIBALH leads to formation of the naphthyridoindole 18. Compound 18 isomerizes in aqueous AcOH to yield pyridocarbazole 3. Finally, closure of ring E and subsequent reduction of the dithiane ring produces aspidospermidine. Pyridocarbazoles 2 and 10 were prepared as models.     

Enantioselective synthesis of (2R,3R)- and (2S,3S)-2- [(3-chlorophenyl)-(2-methoxyphenoxy)methyl]morpholine

The enantioselective synthesis of the (R,R)- and (S,S)-enantiomers of 1 from commercially available 3-chlorocinnamic acid is reported. The Sharpless asymmetric epoxidation was used to establish the stereocenters in the synthesis of both enantiomers of 1.     

First Enantioselective Synthesis of (2R,3R)-and(2S,3S)-2-(4-hydroxyphenyl)-3-hydroxymethyl-1,4-benzodioxan-6-carbaldehyde

Numerous lignans containing 1,4-benzodioxane nucleus represent a class of natural products with cytotoxic and hepatoprotective activities1,2. Recently we have reported the racemic total synthesis of sinaiticin, a flavonolignan of the 1,4-benzodioxane type which was isolated from sinaiticum leaves found in sinai region of Egypt, using 2-(4-hydroxyphenyl)-3-hydroxymethyl-1,4-benzodioxan-6-carbaldehyde as the key interme-diate3,4. This species exhibits significant inhibitory activity against the …     

(2R，3R)-和(2S，3S)-2-(4-羟基-3-甲氧基)-3-羟甲基-1，4-苯并二氧六环-6-醛的对映选择性合成

1,4-苯并二氧六环木脂素类天然产物多数具有增加胆碱乙酰化酶和抗肝毒等活性 ,其活性主要源于 1 ,4-苯并二氧六环官能团 [1] . 1 ,4-苯并二氧六环木脂素的消旋全合成已有报道 [2 ] ,但其不对称合成还是空白[3] .我们发展了一条对映选择性合成 1 ,4-苯并二氧六环木脂素的简捷有效的路线 .基于前面的工作 [4 ] ,我们发现 1 ,4-苯并二氧六环醛类衍生物是合成此类天然产物的关键中间体 ,选择 2 - (4-羟基- 3-甲氧基 ) - 3-羟甲基 - 1 ,4-苯并二氧六环 - 6-醛 (1 )作为目标分子 ,其合成路线如下 :Reagents and conditions:( ) Me OH,H2 SO4,9…     

Enantioselective Catalysis CXLI [1]. Tridentate Ligands with 1-(Pyridin-2-yl)ethylamine as Chiral Building Block in the Enantioselective Transfer Hydrogenation of Acetophenone

Summary.  A series of novel tridentate ligands with nitrogen and oxygen donor sites was synthesized starting from enantiomerically pure (S)- and (R)-1-(pyridin-2-yl)ethylamine, the preparation and resolution of which was developed. The new optically active ligands were tested as in situ catalysts together with Ru(PPh₃)₃Cl₂ in the enantioselective transfer hydrogenation of acetophenone with isopropanol. The secondary amine ligand (S)-2,4-di-tert-butyl-6-(1-(pyridin-2-yl)ethylamino)methylphenol gave the best results with almost quantitative conversion and 47%ee. Received August 17, 2001. Accepted August 27, 2001     

Highly Enantioselective Hetero-Diels-Alder Reaction of 1,3-Bis(silyloxy)-1,3-dienes with Aldehydes Catalyzed by Chiral Disulfonimide

Bulking up with F: The title reaction proceeds using 1?mol?% of the new perfluoroisopropyl chiral disulfonimide catalyst 1 to deliver several 2,6-disubstituted and 2,5,6-trisubstituted dihydropyrones in good yields and with excellent enantiomeric ratios. The utility of this methodology is illustrated with the first enantioselective synthesis of a potent aromatase inhibitor.     

Eleuthesides and their analogs: IV. Synthesis of (1R,5R,6S)-6-(1,3-dithian-2-yl)-1-(2-hydroxyethyl)-5-methylcyclohex-3-ene and its O-tert-butyldimethylsilyl derivative

Two schemes for the preparation of chiral alcohols as key synthons for the synthesis of eleutheside analog at the A ring have been developed on the basis of the Diels-Alder adduct of levoglucosenone with piperylene.     

2-(1,3-亚丙二硫)亚甲基-3-羰基丁酸作为硫醇替代试剂在缩硫醛/酮化反应中的应用

探讨了以2-(1,3-亚丙二硫)亚甲基-3-羰基丁酸作为硫醇替代试剂,乙醇作溶剂的缩硫醛/酮化反应.实验结果表明,该硫醇替代试剂能与各类醛、酮化合物快速、顺利地进行缩硫醛/酮化反应,以较高的产率生成相应的1,3-二噻烷类化合物.同时,该缩硫醛/酮化反应对不同的醛、酮化合物具有较高的化学选择性.     

Determination of the Absolute Configuration of Dimethyl (2S,3S)-2-Allyl-3-hydroxyglutarate: A Chiral Building Block for Preparing Branched-Chain Nucleoside Analogues

A yeast-catalyzed reduction of dimethyl (2S,3S)-2-allyl-3-hydroxyglutarate is the key step in the preparation of bis-homo, branched-chain nucleoside analogues. To establish unambiguously the stereochemical course of the microbial reaction, the product has been converted to a derivative esterified with camphanoyl chloride, and a crystal structure of the derivative solved.