α,β,γ,δ-四-{4-13-(9-(4-(3-(9-(4-(2-(5,5-二酰氧基甲基-1,3-二噁烷基))))苯基-2,4,8,10-四氧杂螺[5.5]十一烷基)))苯基-2,4,8,10-四氧杂螺[5.5]十一烷基]}苯基卟啉星形化合物的合成

以对苯二甲醛、丙二腈、季戊四醇和毗咯为原料,合成了含有螺环结构单元的中间体3-[4-(2,2-二氰基)乙烯基]苯基-9-(4-甲酰基)苯基-2,4,8,10-四氧杂螺[5.5]十一烷(3)和α,β,γ,δ-四-(4-甲酰基苯基)卟啉(4).4与过量的季戊四醇反应,得到α,β,γ,δ-四-{4-[2-(5,5-二羟甲基-1,3-二噁烷基)]}苯基卟啉(5),5与3的反应产物经10%NaOH处理后,再与过量的季戊四醇反应,得到α,β,γ,δ-四-{4-[3-(9-(4-(3-(9-(4-(2-(5,5-二羟甲基-1,3-二噁烷基))))苯基一2,4,8,10.四氧杂螺[5.5]十一烷基)))苯基-2,4,8,10-四氧杂螺[5.5]十一烷基]]苯基卟啉(6),6与乙酐、丙酐、苯甲酰氯反应,得到α,β,γ,δ-四-{4-[3-(9-(4-(3-(9-(4-(2-(5,5-二乙酰氧基甲基-1,3-二噁烷基))))苯基-2,4,8,10-四氧杂螺[5.5]十一烷基)))苯基-2,4,8,10-四氧杂螺[5.5]十一烷基])苯基卟啉(7),α,β,γ,δ-四-{4-[3-(9-(4-(3-(9-(4-(2-(5,5-二丙酰氧基甲基-1,3-二噁烷基))))苯基.2,4,8,10-四氧杂螺[5.5]十一烷基)))苯基-2,4,8,10-四氧杂螺[5.5]十一烷基]}苯基卟啉(8)和α,β,γ,δ-四-{4-[3-(9-(4-(3-(9-(4-(2-(5,5-二苯甲酰氧基甲基-1,3-二噁烷基))))苯基-2,4,8,10-四氧杂螺[5.5]十一烷基)))苯基-2,4,8,10-四氧杂螺[5.5]十一烷基]}苯基卟啉(9)等三种卟啉星形化合物.中间体1～6和星形化合物7～9均进行了IR,1H NMR,MS和元素分析等结构表征.对影响反应的诸因素进行了讨论.     

二代螺环树形化合物1,2,3,4,5,6,7,8,9,10,11,12-十二氢-2,2;6,6;10,10-三[3,3-二(烷氧羰基)-1,1-环亚丁基二甲氧基]三亚苯基的合成

以1,4-环己二酮、丙二酸二乙酯及多元醇等为原料, 经过两次“一锅煮”法合成了六种二代螺环树形化合物1,2,3,4,5,6,7,8,9,10,11,12-十二氢-2,2;6,6;10,10-三[3,3-二(烷氧羰基)-1,1-环亚丁基二甲氧基]三亚苯基螺环树形化合物, 其中烷氧基为异戊氧基、三羟甲基甲氧基、2,2-二溴甲基-3-羟丙氧基、2,2-二羟甲基丙氧基、二羟甲基膦甲氧基和(N-羟甲基-N-二羟甲基氨基乙基)甲氧基. 利用IR, NMR, MS和元素分析对合成的化合物进行了结构认证, 对影响反应的因素进行了讨论.     

7-(羟甲基)-8-氮杂螺[4.5]癸烷-8-羧酸叔丁酯的合成

以8-氮杂螺[4.5]癸烷-7,9-二酮为原料,通过酰胺还原、N-Boc保护、甲酰化、醛基四步反应还原反应合成得到目标化合物7-(羟甲基)-8-氮杂螺[4.5]癸烷-8-羧酸叔丁酯,总收率29.8％.反应中间体及产物结构经1 H NMR和ESI-MS确证,同时对每步反应条件进行讨论.该研究提供了一种新结构的含氮螺环化合...     

季戊四醇双缩脂肪族醛(酮)螺环化合物的合成

以脂肪族醛(酮)为原料,对甲苯磺酸为催化剂,在环己烷中回流分水反应合成了一系列季戊四醇双缩脂肪族醛(酮)螺环化合物(3a~3l),其中3,9-二甲基-3,9-二丁基-2,4,8,10-四氧杂螺[5.5]十一烷(3i)和3,7,11,15,18,21-六氧杂三螺[5.2.2.512.29.26]二十一烷(3k)为新化合物,其结构经1H NMR,13C NMR和ESI-MS表征。     

生物碱Actinophyllic Acid三环中间体的不对称合成

以(S)-3-(2,2-二甲基-5-(3-甲基-1H-吲哚-2-基)-1,3-二氧杂环己烷-5-基)吡咯烷-2-酮为原料,经吡咯烷酮还原开环、串联的氢化脱保护/分子内还原胺化反应等关键步骤,合成了吲哚生物碱actinophyllic acid的A/B/C环手性中间体(S)-3-(2-(2-氯乙酰氨基)-2′,2′-二甲基-1,2,3,4,5,7-六氢螺[氮杂环辛烷并[4,3-b]吲哚-6,5′-[1,3]二氧杂环己烷]-5-基)-3-丙酮酸甲酯（9）; 9可在氧化条件下转化为A/B/G环中间体(S)-7-(2-(2-氯乙酰氨基)乙基)-2′,2′-二甲基-8-氧代-7,8-二氢-5-H-螺[环庚烯并[b]吲哚-6,5′-[1,3]二氧杂环己烷]-9-甲酸酯（10）。该合成路线涉及9个新化合物,其结构经¹H NMR,¹³C NMR, 2D NMR和LC-MS(ESI)表征。     

新型螺双二氢茚二酚衍生物的合成

螺双二氢茚二酚(SPINOL)与N-溴代丁二酰亚胺经溴代反应制得6,6'-二溴-螺双二氢茚二酚(1);1与叔丁基二甲基硅基三氟甲磺酸(TBSOTf)经醚化反应得6,6'-二溴-7-羟基-7'-叔丁基二甲硅氧基-1,1'-螺二氢茚(2);SPINOL经羟基保护后与碘甲烷经双甲基化反应制得6,6'-二甲基-7,7'-双(1-甲氧甲氧基)-1,1'-螺二氢茚(4);4经脱保护后再与TBSOTf经醚化反应合成了6,6'-二甲基-7-羟基-7'-叔丁基二甲硅氧基-1,1'-螺二氢茚(6)。2和6为新化合物,其结构经1H NMR,13C NMR和HR-ESI-MS表征。     

贫电子环丙烷衍生物与甲醇的反应

顺-1-呋喃乙酰基-2-对位取代苯基-6,6-二甲基-5,7-二氧-螺-[2,5]-4,8-辛二酮和顺-1-噻吩乙酰基-2-对位取代苯基-6,6-二甲基-5,7-二氧-螺-[2,5]-4,8-辛二酮与甲醇于封管中80℃反应72 h得到β-呋喃甲酰基-γ-甲氧基-γ-对取代苯基-丁酸甲酯及β-噻吩甲酰基-γ-甲氧基-γ-对取代苯基-丁酸甲酯,其结构经1H NMR,13C NMR,IR,MS及APT。讨论了反应机理。     

螺环三代树形大分子化合物的合成

以对苯二甲醛单缩醛与季戊四醇反应得到了2,4,8,10-四氧杂-2,9-二(4-二氰基乙烯基苯基)螺[5.5]十一烷(1), 经水解, 再与丙二腈反应, 制备了中间体2,4,8,10-四氧杂-2-(4-二氰基乙烯基苯基)-9-(4-甲酰基苯基)螺[5.5]十一烷(3). 8-(4-氧代环己烷基)-1,4-二氧杂螺[4.5]癸烷经芳构化形成2,6,10-三-(4-氧代环己烷基)-1,2,3,4,5,6,7,8,9,10,11,12-十二氢苯并[l]菲(4), 再与甲醛进行羟醛缩合, 制成了2,6,10-三-(4-羟基-3,3,5,5-四羟甲基环己烷基)-1,2,3,4,5,6,7,8,9,10,11,12-十二氢苯并[l]菲(5), 将5与过量的3反应, 得到了目标树形大分子化合物2,6,10-三-{15-(3,11-二(-4-(3-((9-(4-二氰基乙烯基)苯基)2,4,8,10-四氧杂螺[5.5]十一烷基)))-7-羟基-二螺[5.1.5.3]十六烷基)}-1,2,3,4,5,6,7,8,9,10,11,12-十二氢苯并[l]菲(6), 收率为18.1%. 产品结构经IR, 1H NMR, MS和元素分析进行了表征. 对影响反应的因素进行讨论.     

1,3,5,7-四异氰氧基乙基-1,3,5,7-四甲基环四硅氧烷合成及结构表征

以丙烯酸和1,3,5,7-四甲基环四硅氧烷(D4H)等为初始原料,经酯化、硅氢加成反应制得1,3,5,7-四(三甲基硅氧羰丙基)-1,3,5,7-四甲基环四硅氧烷(2),水解2制得1,3,5,7-四羧丙基-1,3,5,7-四甲基环四硅氧烷(3),3经Staudinger反应和Curtius重排反应制得1,3,5,7-四异氰氧基乙基-1,3,5,7-四甲基环四硅氧烷(4).反应总收率为14.5%,化合物结构经1H NMR,29Si NMR,IR,MS和HRMS确证.     

螺环倍半萜(±)-茅苍术醇和(±)-沉香螺醇的改进合成

以2,4-二氧代戊酸甲酯(1)和1,5-二甲基-6-亚甲基环己烯(2)为原料,通过[2+2]光环加成和retro-Benzilicacid重排,合成了具有螺[4,5]癸烷结构的岩兰烷基本碳架的化合物3.用锌粉选择还原五元环上碳碳双键得螺环二酮(4),对环外羰基实施保护并将环上酮基转化为亚甲基得到重要的合成前体6,经与甲基溴化镁的格氏反应生成混合的标题化合物.利用羟基和异氰酸苯酯的反应生成一对N-苯基氨基甲酸酯异构体(12),二者分离后经四氢铝锂还原,完成了螺环倍半萜(±)-茅苍术醇和(±)-沉香螺醇的全合成.     

Enantioselective Synthesis of Ethyl 4,5,7,8,9‐Penta‐O‐acetyl‐2,6‐anhydro‐ 3‐deoxy‐D‐erythro‐L‐gluca‐nononate: a 2‐Monodeoxygenated Derivative of `2‐Keto‐3‐deoxy‐D‐glycero‐D‐galacto‐nononic Acid'

A study aimed at developing an enantioselective synthesis of the title compound 23 , a 2‐monodeoxy analogue of the naturally occurring (+)‐2‐keto‐3‐deoxy‐D ‐glycero‐D ‐galacto‐2‐nononic acid (KDN), is reported. From D ‐mannose as starting material, the chiral 1,3‐diene 10 , activated by a silyloxy substituent at C(2), was prepared in six steps (Scheme 1). However, the intermediates were often contaminated with varying amounts of by‐products arising from overoxidation during cleavage with periodic acid. An alternative route starting from the inexpensive and readily available D ‐isoascorbic acid ( 12 ), though a little longer than the first, satisfactorily circumvented the purification problem and led to the desired dienes 17 in good yields (scheme 2). The [Co^II(S,S)‐(+)‐salen]‐catalyzed hetero‐Diels‐Alder reactions of the aforementioned dienes with ethyl glyoxylate proceeded smoothly at room temperature, giving the dihydropyrano adducts 18 in moderate yields (Scheme 3). Dihydroxylation of 18a followed by reduction of the keto function gave the desired 4,5‐trans dihydroxy moiety of the KDN framework (Scheme 4, see 21 ). The spectroscopic data of the penta‐O‐acetylated 2‐deoxy‐KDN ethyl ester 23 were consistent with those reported for the corresponding methyl ester derived from natural KDN.     

rac‐5‐Diphenylacetyl‐2,2,4‐trimethyl‐2,3,4,5‐tetrahydro‐1,5‐benzothiazepine and rac‐5‐formyl‐2,2,4‐trimethyl‐2,3,4,5‐tetrahydro‐1,5‐benzothiazepine

rac‐5‐Diphenylacetyl‐2,2,4‐trimethyl‐2,3,4,5‐tetrahydro‐1,5‐benzothiazepine, C₂₆H₂₇NOS, (I), and rac‐5‐formyl‐2,2,4‐trimethyl‐2,3,4,5‐tetrahydro‐1,5‐benzothiazepine, C₁₃H₁₇NOS, (II), are both characterized by a planar configuration around the heterocyclic N atom. In contrast with the chair conformation of the parent benzothiazepine, which has no substituents at the heterocyclic N atom, the seven‐membered ring adopts a boat conformation in (I) and a conformation intermediate between boat and twist‐boat in (II). The molecules lack a symmetry plane, indicating distortions from the perfect boat or twist‐boat conformations. The supramolecular architectures are significantly different, depending in (I) on C—H...O interactions and intermolecular S...S contacts, and in (II) on a single aromatic π–π stacking interaction.     

O‐Benzyl‐N‐tert‐butoxy­carbonyl‐N‐methyl‐l‐tyrosine

The crystal structure of the title compound, alternatively called 3‐[4‐(benzyl­oxy)­phenyl]‐2‐(N‐tert‐butoxy­car­bonyl‐N‐methyl­amino)­propi­onic acid, C₂₂H₂₇NO₅, has been studied in order to ex­amine the role of N‐methyl­ation as a determinant of peptide conformation. The conformation of the tert‐butoxy­carbonyl group is trans–trans. The side chain has a folded conformation and the two phenyl rings are effectively perpendicular to one another. The carboxyl­ate hydroxyl group and the urethane carbonyl group form a strong intermolecular O—H?O hydrogen bond.     

Neue molekulare Indium‐Zinn‐Sauerstoff‐ und Indium‐Zinn‐Natrium‐Sauerstoff‐Chlor‐Cluster

Abstract. The five‐membered heteroelement cluster THF · Cl₂In(O^tBu)₃Sn reacts with the sodium stannate [Na(O^tBu)₃Sn]₂ to produce either the new oxo‐centered alkoxo cluster ClInO[Sn(O^tBu)₂]₃ ( 1 ) (in low yield) or the heteroleptic alkoxo cluster Sn(O^tBu)₃InCl₃Na[Sn(O^tBu)₂]₂ ( 2 ). X‐ray diffraction analyses reveal that in compound 1 the polycyclic entity is made of three tin atoms which together with a central oxygen atom form a trigonal, almost planar triangle, perpendicular to which a further indium atom is connected through the oxygen atom. The metal atoms thus are arranged in a Sn₃In pyramid, the edges of which are all saturated by bridging tert‐butoxy groups. The indium atom has a further chloride ligand. Compound 2 has two trigonal bipyramids as building blocks which are fused together at a six coordinate indium atom. One of the bipyramids is of the type SnO₃In with tert‐butyl groups on the oxygen atoms, while the other has the composition InCl₃Na with chlorine atoms connecting the two metals. The sodium atom in 2 has further contacts to two plus one alkoxide groups which are part of a[Sn(O^tBu)₂]₂ dimer disposing of a Sn₂O₂ central cycle. The hetero element cluster in 2 thus combines three closed entities and its skeleton SnO₃InCl₃NaO₂Sn₂O₂ consists of three different metallic and two different non‐metallic elements.     

Synthesis of Novel 3‐Acetyl‐2‐Aryl‐5‐(3‐Aryl‐1‐Phenyl‐Pyrazol‐4‐yl)‐2,3‐Dihydro‐1,3,4‐Oxadiazoles

A series of novel pyrazolyl‐substituted 1,3,4‐oxadiazole derivatives ( 4a‐4o ) were prepared by cyclization of the intermediate N′‐((3‐aryl‐l‐phenyl‐pyrazol‐4‐yl)methylene)arylhydrazide with acetic anhydride. The structures of the new compounds were confirmed by IR, ¹H NMR, MS and elemental analysis. Furthermore, preliminary bioassay of some of the title compounds indicated that they exhibited moderate inhibition against HIV‐1 PR.     

5‐Acetyl‐2‐amino‐6‐methyl‐4‐phenyl‐4H‐pyran‐3‐carbonitrile and 2‐amino‐5‐benzoyl‐6‐methyl‐4‐phenyl‐4H‐pyran‐3‐carbonitrile acetonitrile solvate

The syntheses, X‐ray structural investigations and calculations of the conformational preferences of the carbonyl substituent with respect to the pyran ring have been carried out for the two title compounds, viz. C₁₅H₁₄N₂O₂, (II), and C₂₀H₁₆N₂O₂·C₂H₃N, (III), respectively. In both mol­ecules, the heterocyclic ring adopts a flattened boat conformation. In (II), the carbonyl group and a double bond of the heterocyclic ring are syn, but in (III) they are anti. The carbonyl group forms a short contact with a methyl group H atom in (II). The dihedral angles between the pseudo‐axial phenyl substituent and the flat part of the pyran ring are 92.7 (1) and 93.2 (1)° in (II) and (III), respectively. In the crystal structure of (II), inter­molecular N—H⋯N and N—H⋯O hydrogen bonds link the mol­ecules into a sheet along the (103) plane, while in (III), they link the mol­ecules into ribbons along the a axis.     

Synthesis of 15‐Cyano‐12‐oxopentadecano‐15‐lactone and 15‐Cyano‐ 12‐oxopentadecano‐15‐lactam

15‐Cyano‐12‐oxopentadecano‐15‐lactone was synthesized in 59% total yield starting from 2‐nitrocyclododecanone by Michael addition to acrylaldehyde, followed by reaction with trimethylsilylcyanide, hydrolysis, ring‐expansion, and Nef reaction. A two‐step, one‐pot synthesis of intermediate 2‐hydroxy‐4‐(1‐nitro‐2‐oxycyclododecyl)butanenitrile from 3‐(1‐nitro‐2‐oxocyclododecyl)propanal was developed and the conditions for the Nef reaction were studied. 15‐Cyano‐12‐oxopentadecano‐15‐lactam was synthesized in 40% total yield starting from 2‐nitrocyclododecanone by Michael addition to acrylaldehyde, followed by Strecker reaction, ring‐expansion, and Nef reaction. The conditions for the Strecker and Nef reactions were studied. The structures of the target compounds, intermediates, and by‐product were characterized by IR, ¹H‐ and ¹³C‐NMR, and elemental analysis or MS.     

1H and 13C NMR analysis of 2‐acetamido‐3‐mercapto‐3‐methyl‐N‐aryl‐butanamides and 2‐acetamido‐3‐methyl‐3‐nitrososulfanyl‐N‐aryl‐butanamide derivatives

The complete assignment of the ¹H and ¹³C NMR spectra of various 2‐acetamido‐3‐mercapto‐3‐methyl‐N‐aryl‐butanamides and 2‐acetamide‐3‐methyl‐3‐nitrososulfanyl‐N‐aryl‐butanamides with p‐methoxy, o‐chloro and m‐chloro substituents is reported. Copyright © 2013 John Wiley & Sons, Ltd.