（2R,3S）—2甲基—3—羟基戊酸甲酯的手性合成

１引言烟草甲ＬａｊｓｔｏｄｅｒｍａｓｅｒｒｉｃｏｒｎｅＦａｂｒ。ｉｎｓ是一种主要危害烟草、香烟、干燥植物以及谷物、面粉的农业害虫。这种害虫在我国主要分布在淮河以南地区以及世界各地的温暖地带［‘］。（２,３Ｓ）－２一甲基一３一羟基成酸甲酯是我们设计的合成烟草甲性信息素的一个重要中间体。我们以丙快醇为基本原料合成了该化合物。丙炔醇参照文献ｌ’］方法制得２一戊炔一ｌ一醇２,催化还原条件下,炔键可被部分加氢得到（Ｑ－２一戊烯一卜醇３。在四异丙氧基钛、Ｄ－（）一酒石酸＄［Ｊ４Ａ分于筛催化条件下,顺式烯丙醇…     

（2S,3R）—谷象虫聚集信息素的合成

（２Ｓ，３Ｒ）┐谷象虫聚集信息素的合成黄锦霞＊李焰马兴泉陈祖兴徐章煌（湖北大学化学系武汉４３００６２）关键词（２Ｓ，３Ｒ）－谷象虫聚集信息素，合成，不对称顺式醇醛缩合反应，Ｎ－莰烷－磺内酰胺１９９７－０７－１４收稿，１９９７－０９－２９修回湖北省自然...     

Synthesis of molecular ferromagnetics [R3R′X]MCr(C2O4)3 (X = N,R = Bun,R′ = Prn,Et, Me; X = P,R = Ph,R′ = Bun; M = Mn,Fe, Co,Ni, Cu)

The synthesis, IR spectra, and the temperatures of the transition into a ferromagnetic state (T _c) of layered ferromagnetics [R₃RX[MCr(C₂O₄)₃ (M = Mn, Fe, Co, Cu, and Ni) with the [Ph₃BuP]⁺, [Bu₃RN]⁺ (R = Pr, Et, and Me) cations capable of subsequently changing the distances between metallooxalate layers have been considered. The temperatureT _c has been found to be independent of the size of the organic cation. It is believed that the determining factors in the transition to a ferromagnetic state are exchange interactions inside the metallooxalate layer.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 2327–2330, September, 1996.     

Synthesis of （2R,4R）—2—N—tert—Butyloxycarbonyl Amino—4,5—epoxido—valeric Acid Methyl Ester

The stereoselective synthesis of (2R,4R)-2-N-tert-butyloxycarbonyl amino-4,5-epoxido-valeric acid methyl ester 8,which is the key intermediate for the synthesis of (2′S,2R)-3-trans-nitrocyclopropyl-alanine,was first accomplished.     

由孕甾-3S,5R,6R,16S,20S-五醇合成黄体酮

首次利用薯蓣皂甙元降解产物, 孕甾-3S,5R,6R,16S,20S-五醇(3)完成了黄体酮的合成. 孕甾-3S,5R,6R,16S,20S-五醇可方便地通过薯蓣皂甙元经由30%双氧水原地产生的过酸氧化降解得到. 它经过缩酮化反应、乙酰化反应和串联的脱缩酮-溴代乙酰化反应被转化成关键合成中间体16R-溴孕甾-3S,5R,6R,20S-四醇-3,6,20-三乙酸酯(6). 化合物6经锌粉还原、C-3乙酰氧基选择性水解氧化反应和C-5羟基消除反应生成6R,20S-二乙酰氧基孕甾-4-烯-3-酮(10). 化合物10经C-6乙酰氧基还原和C-20乙酰氧基水解-氧化生成目标分子黄体酮. 合成经10步反应, 反应总收率达45.1%.     

Resolution of 1-n-propoxy-3-methyl-3-phospholene 1-oxide by diastereomeric complex formation using TADDOL derivatives and calcium salts of O,O′-dibenzoyl-(2R,3R)- or O,O′-di-p-toluoyl-(2R,3R)-tartaric acid

1-n-Propoxy-3-methyl-3-phospholene 1-oxide was prepared in optically active form by extending resolution methods applying (−)-(4R,5R)-4,5-bis(diphenylhydroxymethyl)-2,2-dimethyldioxolane (‘TADDOL’) and (−)-(2R,3R)-α,α,α′,α′-tetraphenyl-1,4-dioxaspiro[4.5]decan-2,3-dimethanol (‘spiro-TADDOL’), as well as the acidic and neutral Ca²⁺ salts of (−)-O,O′-dibenzoyl- and (−)-O,O′-di-p-toluoyl-(2R,3R)-tartaric acid. In one case, the diastereomeric complex could be identified by single crystal X-ray analysis. The absolute P-configuration of the enantiomers of the phospholene oxide was also determined by CD spectroscopy.     

Asymmetric Synthesis of (-)-(2R,3R,6S)-Irnigaine

Introduction　　Asarelativelynewmemberofnaturalalkaloidswith2 ,6 disubstituted 3 piperidinolskeleton ,irnigaine 1wasisolatedfromthetubersofArisarumVulgare (Araceae)in1995byMelhaouiandBode .1Itsstructureandrelativeconfigurationswereelucidatedby1HNMRstudiesandtheabsoluteconfigurationwasproposedonthebasisofitsopti calrotation .1Soonafterthen ,Meyerandhisco workersreportedthefirstsynthesisof (- ) (2R ,3R ,6S) irni gaineandtheconfigurationconfirmation .Althoughtheirsynthesisroutewasshortan…     

A Convenient Method for Synthesis of Novel Cyclic Ethers (1R,2R,3R,5S,7S,9R,12R)-3-(t-Butyldimethylsilyl)oxy-7-methoxymethyl-oxy-2,10-dimethyl-12-oxatricyclo [7.2.1.0~(5,12)] dodecane

Coloradocin, a novel macrolide antibiotic from cultures of Actinoplanes coloradoensis1exhibits activity against pathogenic anaerobic and microaerophilic species2. Because itslow toxicity and substantial oral activity3, , as well as its unusual structure5, several 4research groups initiated approaches towards the synthesis of coloradocin6, whichculminated in the synthesis of 18-deoxynargenicin A1 by Kallmerten et al.7. …     

1,3,3a,5—四苯基—3a,4,5,11—四氢—3H,6H—1,2,4—三唑并（ …

通过２，４－二苯基－２，３－二氢－１Ｈ－１，５－苯并二氮杂Ｚｕｏ与苯甲酰氯苯腙的（２＋３）环加成反应制备了标题化合物，用Ｘ射线单晶衍射仪测定了其晶体结构，晶体属正交晶系，空间群为Ｆｄｄ２．晶胞参数；ａ＝１．７６２８（４）ｎｍ，ｂ＝５．７５１２（１２）ｎｍ，ｃ＝１．０２２７ｎｍ，Ｖ＝１０．３６８（５）ｎｍ＾３，Ｚ＝１６，Ｄｃ＝１．２６２ｇ．ｃｍ＾－３，μ＝０．０７５ｍｍ＾－１，Ｆ（０００）＝４１６０     

Asymmetric Synthesis of （ － ）－（2R ,3R, 6S ）－Irnigaine

Asymmetric synthesis of irnigaine was achieved starting from an enantiopure β-amino ester 5 using the condensation of amino al-cohol 2 with acetylacetone and the subsequent intramolecular cycllzation as the key steps.     

亚胺膦R3PNH（R=CH,Cl）的极性及P—N键性质的理论研究

用从头算方法在Ｂ３ＬＹＰ／６－３１Ｇ＊＊水平上对亚胺膦Ｒ３ＰＮＨ（Ｒ＝ＣＨ３,Ｃｌ）进行了理论计算研究。结果表明这两种亚胺膦的极性,Ｐ－Ｎ键性质及分子轨道存在明显差异,亚胺膦（ＣＨ３）３Ｐ＝ＮＨ及其Ｐ－Ｎ键的极性很强,而Ｃｌ３Ｐ＝ＮＨ的极性则较弱。与Ｃｌ３Ｐ＝ＮＨ相比（ＣＨ３）３Ｐ＝ＮＨ可能是较好的类Ｗｉｔｔｉｎｇ反应试剂。