金鸡钠碱催化烯胺的不对称C-亚磺酰化反应

以金鸡钠碱催化烯胺的不对称C-亚磺酰化反应,产物(E,Z)-N-苄氧羰基-2-苯亚磺酰基-1-苯基丙烯胺[(E,Z)-4],收率71%,立体选择性E:Z=3:2,其中(E)-4和(Z)-4的对映选择性分别为75%ee和93%ee。     

(Z)-4-(2-溴乙烯基)苯磺酸酚酯的“一锅法”合成

以3-(4-氯磺酰苯基)-2,3-二溴丙酸和酚为原料,以CH2C12-DMF(v/v:2/1)为混和溶剂,加入Et3N,在0℃-室温条件下“一锅法”反应12h,即可高立体选择性地合成(Z)4-(2-溴乙烯基)苯磺酸酚酯(Z/E:＞99/1),收率78.5-81.0％.该化合物可以简便的转化为(Z)-4-(2-溴乙烯基)...     

第五、六族元素的有机化合物在有机合成中应用的研究 ⅩⅩⅩⅢ.氰基亚甲基三苯基膦、胂与2-全氟炔酸甲酯的反应以及3-全氟烷基-4-氰基-3-丁烯酸甲酯的立体选择性合成

氰基亚甲基三苯基胂(1)与2-全氟炔酸甲酯(2)反应,生成加合产物3.通过3的水解,立体选择性地合成了3-全氟烷基-4-氰基-3-丁烯酸甲酯[5(Z),6(E)],Z:E约为95∶5。氰基亚甲基三苯基膦(7)与2亦可反应,生成加合产物8和9,总产率在90%左右。8与9的比例受反应介质极性的影响,若溶剂极性增大,则有利于8的生成。     

乙酰丙酮氧钒催化氧化α-蒎烯一步转化成龙脑烯醛

以乙酰丙酮氧钒为催化剂,过氧化氢为氧化剂,研究了由α-蒎烯直接合成龙脑烯醛的反应。考察了溶剂、温度、催化剂用量、反应时间等因素对催化性能的影响。结果表明,乙酰丙酮氧钒与H2O2反应得到的高价态V5+是优良的氧化还原-Lewis酸双功能催化剂,易使α-蒎烯经氧化、2,3-环氧蒎烷异构得到龙脑烯醛。在n(H2O2):n(α-蒎烯):n(乙酰丙酮氧钒)=2.5:1:0.01、反应温度为20℃、丙酮为溶剂、反应2h条件下,α-蒎烯转化率为50.2%,龙脑烯醛的选择性达58.7%,反应6h后α-蒎烯转化率可达73.0%,主要产物龙脑烯醛和马鞭草烯酮的选择性分别为47.2%和13.2%。     

第五、六族元素的有机化合物在有机合成中应用的研究 XXXIII: 氰基亚甲基三苯基膦、胂与2-全氟炔酸甲酯的反应以及3-全氟烷基-4-氰基-3-丁烯酸甲酯的立体选择性合成

氰基亚甲基三苯基胂(1)与2-全氟炔酸甲酯(2)反应,生成加合产物2-三苯胂基-3-全氟烷基-4-氰基丁烯-3-酸甲酯(3)通过3的水解,立体选择性地合成了3-全氟烷基-4-氰基-3-丁烯酸甲酸甲酯[5(Z),6(E)],Z:E约为95:5.氰基亚甲基三苯基膦(7)与2亦可反应,生成加合产物2-三苯基膦叉-3-全氟烷基-4-氰基丁烯-3-酸甲酯的顺式和反式异构体(8)和(9).总产率在90%左右.8与9的比例受反应介质极性的影响,若溶剂极性增大,则有利于8的生成.     

β-榄香烯氨基酸衍生物的合成

以β-榄香烯为起始原料,在未对氨基酸进行保护的条件下,以乙醇和水的混合物作溶剂(V(乙醇):V(水)的最佳比为4: 1),与7种不同的氨基酸在碱性条件下于66 ℃反应,合成了一系列β-榄香烯单取代氨基酸衍生物,并用IR、 1H NMR及HRMS测试技术对其结构进行了表征. 探讨了反应温度对反应收率的影响,结果表明,反应温度以66 ℃为宜,温度太高副产物较多,温度太低,反应难以进行,次氯酸钠用量以参加反应β-榄香烯物质量的2倍为宜..     

氢氧化铯催化下,二芳基二硒醚对端炔的加成:高选择性合成(Z)-1,2-二芳硒基烯

氢氧化铯催化下,以商业THF作溶剂,端炔与二芳基二硒醚在氮气保护下,25或35℃时反应,立体选择地生成(Z)-1,2-二芳硒基烯.     

钙伯三醇的关键中间体——麦角甾烷-5，7（E），10（19）-三烯-6（S）-二氧化硫的合成

麦角甾烷-5,7(E),10(19),22(E)-四烯-6(S)-二氧化硫(1)经臭氧化反应合成了钙伯三醇(MC903)的重要中间体--麦角甾烷-5,7(E),10(19)-三烯-6(S)-二氧化硫(2),其结构经1H NMR和13C NMR表征.较佳的臭氧化反应条件为:1 1.0 mmol,溶剂为V(二氯甲烷):V(甲醇)=4:1,于-65℃～-78℃反应12 min.在此条件下,2中醛基α-位的差相异构化降至最低程度,产率90%.对差相异构化的机理进行了讨论.     

酸催化α-细辛脑二聚反应及其产物抗癌活性研究

以E-1-(2,4,5-三甲氧基苯基)-2-丙烯(α-细辛脑)为原料,酸催化选择性合成脱碳木脂素类化合物a及二氢化茚类化合物b,其结构经核磁﹑质谱和元素分析表征确认.研究了催化剂种类、反应溶剂和温度等条件对两种化合物产率比的影响,45℃时,HCl为催化剂,乙醇为溶剂,化合物a/b的总收率为98%(a:41%,b:57%);30℃时,AlCl3为催化剂,乙醇为溶剂,化合物a的产率可达75%,没有b生成,对a的选择性为100%;45℃时,以BF3Et2O溶液为催化剂,CH2Cl2为溶剂,化合物a的产率为20%,化合物b的产率可达60%.采用MTT法,分别评价了化合物a/b对四种癌细胞(MCF-7,Bel-7402,A549及Hela)的抑制作用,结果表明:化合物a对MCF-7,Hela(IC50值分别为:120.2,117.3μmol L-1),化合物b则对MCF-7,A549(IC50值分别为:66.1,72.4μmol L-1)显示出比相同条件下5-Fu更好的抗癌抑制活性.同时,研究了a/b浓度﹑作用时间对癌细胞抑制率的影响.     

膦、胂叶立德的化学与应用ⅩⅩⅥ.含全氟烷基胂叶立德的合成及水解反应研究

报道溴化(α-呋喃甲酰基)甲基三苯基钟(1)在无水碳酸钾存在下,以无水二氯甲烷作溶剂,保持0～5℃下与2-全氟炔酸甲酯(2)反应,高产率地得到加合产物4-(α-呋喃甲酰基)-2-三苯基胂基-3-全氟烷基-3-丁烯酸甲酯(3).加合产物3在V(甲醇):V(水)=9:1溶液中分别于室温、回流和封管120℃三种条件下反应,高产率地得到4-全氟烷基-6-(α-呋喃基)-2-吡喃酮(4)和4-(α-呋喃甲酰基)-3-全氟烷基-3-丁烯酸甲酯(5).化合物4和5可以通过柱层析分离;化合物5为一对Z,E异构体,它们不能通过柱层析分离,但其比例可以由1HNMR估算得到.研究还发现硅胶对该反应具有催化作用,提出并讨论了反应机理.     

Synthesis and Crystal Structure of Nido 11-Vertex Platinaborane [ （PPh3）2PtB10H10-9,10-（H0.7Cl0.3）2]

The reaction of PtCl2（PPh3）2 with closo-[B10H10]^2- in t-BuOH under reflux （70 h） unexpectedly afforded the nido 11-vertex platinaborane [（PPh3）2PtB 10H10-9,10-（H0.7Cl0.3）2] 1, which was characterized by single-crystal X-ray diffraction study. Crystallographic data for 1： C36H41.40B10Cl0.60P2Pt, Mr = 860.49, triclinic system, space group P1, a = 11.255（2）, b = 11.623（2）, c = 17.148（3）A, α = 81.012（2）, β = 88.115（3）, γ=64.322（2）°, V= 1995.4（7）A^3, Z= 2, Dc = 1.432 g/cm^3, μ（MoKα） = 3.662 mm^-1, F（000） = 851, R = 0.0358 and wR = 0.0951. Compound 1 has a nido 11-vertex {PtB10} polyhedral skeleton with the Pt atom lying in the open PtB4 face and further ligating to two PPh3 ligands. 1 is partially chlorinated at positions B（9） and B（10）, and for each chlorine atom an occupancy factor of 0.3 is given by crystallography.     

Synthesis and characterization of 8-(dimethylamino)-1-naphthyl derivatives of aluminum, gallium, and indium

The group 13 dichlorides of formula Ar'MCl2 [Ar' = 8-(dimethylamino)-1-naphthyl (8-(Me2N)C10H6)], M = Al (1), Ga (2), and In (3), have been prepared via the salt elimination reaction of 1 equiv of Ar'Li with MCl3 in toluene solution at -78 degrees C. The reaction of 1 with LiAlH4 in diethyl ether solution at -78 degrees C produced the dihydride [Ar'AlH2]2 (4). The X-ray crystal structures of 1-4 have been determined and show that 1 and 2 are monomeric while 3 and 4 are dimeric in the solid state. The reaction of 1 with RLi in toluene solution at -78 degrees C results in ligand redistribution and formation of Ar'2AlR (R = Me (5), t-Bu (6)). The chloride analogue of 5 and 6, Ar'2AlCl (7), can be prepared directly from the reaction of 2 equiv of Ar'Li with AlCl3 in toluene solution at -78 degrees C. The homoleptic derivative Ar'3Al (8) was obtained when 3 equiv of Ar'Li was employed. Crystal data for 1: monoclinic, space group P2(1), a = 6.534(1) A, b = 10.801(1) A, c = 9.631(2) A, beta = 105.57(2) degrees, V = 654.8(2) A3, Z = 2, R = 0.0453. Crystal data for 2: monoclinic, space group P2(1), a = 6.552(2) A, b = 10.833(2) A, c = 9.601(2) A, beta = 106.05(2) degrees, V = 654.9(3) A3, Z = 2, R = 0.0609. Crystal data for 3: monoclinic, space group P2(1)/c, a = 7.401(2) A, b = 15.746 A, c = 10.801(4) A, beta = 92.37(3) degrees, V = 1257.6(7) A3, Z = 2, R = 0.0712. Crystal data for 4: monoclinic, space group P2(1)/c, a = 13.343(2) A, b = 11.228(2) A, c = 7.505(1) A, beta = 100.64(1) degrees, V = 1105.0(4) A3, Z = 4, R = 0.0560.     

Experimental and Theoretical Investigations of the Formation of the Diazene PhSN=C(H)N=NC(H)=NSPh from HCN(2)(SPh)(3) by a Thiyl-Radical-Catalyzed Mechanism: Identification of the HC(NSPh)(2)(*) Radical and X-ray Structures of HCN(2)(SPh)(3) and PhSN=C(H)N=NC(H)=NSPh

The reaction of HCN(2)(SiMe(3))(3) with benzenesulfenyl chloride in a 1:3 molar ratio produces HCN(2)(SPh)(3) (4) as thermally unstable, colorless crystals. The decomposition of (4) in toluene at 95 degrees C was monitored by UV-visible, (1)H NMR and ESR spectroscopy. The major final products of the decomposition were identified as PhSN=C(H)N=NC(H)=NSPh (5) and PhSSPh. The structures of 4 and 5 were determined by X-ray crystallography. The crystals of 4 are monoclinic, space group P2(1)/a, with a = 9.874(2) ?, b = 19.133(2) ?, c = 10.280(2) ?, beta = 113.37(1) degrees, V = 1782.8(5) ?(3), and Z = 4. The final R and R(w) values were 0.042 and 0.049, respectively. The crystals of 5 are monoclinic, space group P2(1)/n, with a = 5.897(6) ?, b = 18.458(10) ?, c = 7.050(8) ?, beta = 110.97(5) degrees, V = 716(1) ?(3), and Z = 2. The final R and R(w) values were 0.075 and 0.085, respectively. The diazene 5 adopts a Z,E,Z structure with weak intramolecular S.N contacts of 2.83 ?, giving rise to four-membered NCNS rings. During the thermolysis of 4 at 95 degrees C in toluene a transient species (lambda(max) 820 nm) was detected. It decomposes with second-order kinetics to give 5 (lambda(max) 450 nm). The ESR spectrum of the reaction mixture consisted of the superposition of a three-line 1:1:1 spectrum (g = 2.0074, A(N) = 11.45 G), attributed to (PhS)(2)N(*), upon a doublet of quintets (1:2:3:2:1) with g = 2.0070, A(N) = 6.14 G, A(H) = 2.1 G assigned to the radical HCN(2)(SPh)(2)(*). Density functional theory (DFT) calculations for the models of the radical showed the E,Z isomer to have the lowest energy. Thermochemical calculations indicate that the decomposition of HCN(2)(SH)(3) into the diazene (Z,E,Z)-HSN=C(H)N=NC(H)=NSH (and 2 HSSH) is substantially more exothermic (DeltaH = -176.1 kJ mol(-)(1)) than the corresponding formation of the isomeric eight-membered ring (HC)(2)N(4)(SH)(2) (DeltaH = -40.6 kJ mol(-)(1)). These calculations also indicate that the diazene is formed by a mechanism in which the RS(*) radical acts as a catalyst.     

Selenium imides: 77Se NMR investigations of the SeCl2-tBuNH2 reaction and X-ray structures of Se3(NtBu)3, tBuNSe(mu-NtBu)2SO2, and tBuNSe(mu-NtBu)2SeO

The reaction of SeCl2 with tert-butylamine in various molar ratios in THF at -78 degrees C has been investigated by 77Se NMR spectroscopy. In addition to the known Se-N heterocycles Se6(NtBu)2 (1) and Se9(NtBu)6 (2), the acyclic imidoselenium(II) dichlorides ClSe[N(tBu)Se]nCl (4, n = 1; 5, n = 2) and two new cyclic selenium imides [Se3(NtBu)2]n (3, n = 1 or 2) and Se3(NtBu)3 (6) have been isolated and identified. An X-ray analysis shows that 6 is a six-membered ring in a chair conformation with magnitude of d(Se-N) = 1.833 A. Crystal data: 6, trigonal, P3c1, a = 9.8660(3) A, c = 20.8427(7) A, V = 1757.0(1) A3, Z = 6. The 1H, 13C, and 77Se NMR data for 1-6 are reported, and some reassignments of earlier literature data for 1-3 (n = 1) are made. The decomposition of tBuN=Se=NtBu at 20 degrees C in toluene was monitored by 77Se NMR. The major products are 6 and 3. The Se(IV)-N systems tBuNSe(mu-NtBu)2E (7, E = SO2; 8, E = SeO) were prepared by the reaction of a mixture of SeCl4 and excess tBuNH2 with SO2Cl2 or SeOCl2, respectively. Compound 8 is also generated by the cycloaddition reaction of tBuNSeNtBu with tBuNSeO. Both 7 and 8 consist of slightly puckered four-membered rings. The mean terminal and bridging Se-N distances in 7 are 1.665(2) and 1.948(2) A, respectively. The corresponding values for 8 are 1.687(4) and 1.900(4) A, and d(Se=O) = 1.628(4) A. Crystal data: 7, monoclinic, P2(1)/c, a = 18.669(4) A, b = 12.329(2) A, c = 16.463(3) A, beta = 115.56(3) degrees, V = 3418.4(11) A3, Z = 4; 8, triclinic, P1, a = 6.372(1) A, b = 9.926(2) A, c = 14.034(3) A, alpha = 99.320(3) A, beta = 95.764(3) A, gamma = 103.876(3) A, V = 841.3(3) A3, Z = 2.     

膦、胂叶立德的化学与应用26: 含全氟烷基胂叶立德的合成及 水解反应研究

报道溴化α-呋喃甲酰基)甲基三苯基申(1)在无水碳酸钾存在下,以无水二氯甲烷作溶剂,保持0-5℃下与2-全氟炔酸甲酯(2)反应,高产率地得到加合产物4-(α-呋喃甲酰基)-2-三苯基胂基-3-全氟烷基-3-丁烯酸甲酯(3)。加合产物3在V(甲醇):V(水)=9:1溶液中分别于室温、回流和封管120℃三种条件下反应,高产率地得到4-全氟烷基-6-(α-呋喃基)-2-吡喃酮(4)和4-(α-呋喃甲酰基)-3-全氟烷基-3-丁烯酸甲酯(5)。化合物4和5可以通过柱层析分离;化合物5为一对Z,E异构体,它们不能通过柱层析分离,但其比例可以由^1HNMR估算得到。研究还发现硅胶对该反应具有催化作用,提出并讨论了反应机理。     

Synthesis and Structure of N-(E)-Enoyl(-)-bornane-10,2-sultams

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An allyltitanium derived from acrolein 1,2-dicyclohexylethylene acetal and (eta(2)-propene)Ti(O-i-Pr)(2) as a chiral propionaldehyde homoenolate equivalent that reacts with imines with excellent stereoselectivity. An efficient and practical access to optically active gamma-amino carbonyl compounds

A chiral allyltitanium compound 2, prepared in situ by the reaction of optically active acrolein 1,2-dicyclohexylethylene acetal (3) with (eta(2)-propene)Ti(O-i-Pr)(2) (1), reacts with a variety of acyclic and cyclic imines 4 in a regiospecific way to afford alpha-addition products 5 as a mixture of the E- and Z-isomers in good combined yield, where the former is predominant in a ratio of 92:8 to >95:5. The mixture of (E)- and (Z)-5 and pure (E)-5 which could be isolated in several cases were respectively converted to the corresponding beta-amino ester 6 to confirm the absolute configuration and enantiomeric purity. The ee of the newly formed asymmetric center of 5 is more than 78% for the mixture of (E)- and (Z)-5 and more than 96% for pure (E)-5. By taking advantage of the versatility of the vinyl ether moiety in 5, optically active gamma-amino aldehydes 8, gamma-amino aldehyde acetals 7 and 10, gamma-amino acids 9, beta-amino esters 6, and pyrrolidinoisoquinolines 12 were readily prepared. In the reaction of 2 with optically active alpha-silyloxyimine 4n, remarkable double stereodifferentiation was observed; thus, the reaction of 2 derived from (S,S)- or (R,R)-3 provided syn- and anti-5n in a ratio of 55:45 or 0:100, respectively. Meanwhile, the stereochemistry of the product in the reaction of 2 with beta-silyloxyimine 4o was controlled mainly by 2. Thus, the reaction of beta-silyloxyimine 14 with 2 derived from 1 and (R,R)-3 afforded gamma-silyloxyimine 15 with 92% diastereoselectivity, from which 4-amino-6-hydroxypentadecanal dimethyl acetal (13), a key intermediate for the synthesis of batzelladine D, was synthesized.     

酸催化甘油与苯甲醛缩合制备六员环缩醛

比较了对甲苯磺酸（PTSA）、磷钨酸（PWA）、KHSO₄和FeCl₃催化对甘油与苯甲醛的缩合反应收率,及对产物中六元环缩醛5-羟基-2-苯基-1,3-二氧六环(1)与五元环缩醛4-羟甲基-2-苯基-1,3-二氧五环(2)比例的影响。 当以环己烷为带水剂及苯甲醛与甘油的摩尔比为2∶3的情况下,KHSO4为催化剂的缩合产物（1+2）收率较高,为96.8%;PTSA催化的缩合产物中,化合物1的比例最高(m(1)∶m(2)=48.6∶51.4)。 室温下PTSA、PWA、KHSO₄和FeCl₃均可催化化合物2向化合物1的转化。 在-20 ℃下,只有PTSA能催化化合物2向化合物1的转化。 在-20 ℃,PTSA催化化合物[STHZ]2转化成化合物1a,并以晶体形式从苯（40%）-石油醚（60%）中析出。 母液循环转化3次后,化合物1a的累计收率可达91.1%。     

松毛虫性信息素(5Z,7E)-十二碳二烯醇的立体选择性合成

从简单原料乙炔出发,通过炔对丙烯醛的加成反应得到7-溴代-(4Z,6E)-庚二烯醛,再经乙二醇保护、Pd催化偶联、水解、Wittig反应和还原等步骤,立体选择性地得到松毛虫性信息素(5Z,7E)-十二碳二烯醇,其结构通过IR,NMR和MS等技术得到确认.     

高效大量合成AF-5的中间体:(4aR,7R)-1-丁基 -4a-甲基-7-(1-甲基-1-羟乙基)-2(1H)-八氢萘酮

化合物(4 aR,7R)-1-丁基-4 a-甲基-7-(1-甲基-1-羟乙基)-2(1H)-八氢萘酮是合成AF-5的重要中间体,传统方法是在强碱叔丁醇钾的作用下对化合物(4 aR,7R)-4 a-甲基-7-(1-甲基-1-羟乙基)-2(1H)-八氢萘酮进行烷基化反应而得到的.为了使操作更方便、安全,适合大量制备,并提高收率,作者探索了多种碱性条件,并选择氢氧化钾的叔丁醇溶液代替叔丁醇钾,最终使该步烷基化反应可以工业化.