加成化合物

These chemical shifts in the aromatic region of the resulting nucleophilic adduct 2-F were consistent with the counterparts of 9,10-dihydro-9-methoxy-9-(4-methoxyphenyl)-10-methylacridine, 17b which was proven to be the adduct of the 9-phenyl acridinium salt formed with an excess of MeOH (Figure S7 in Supporting Information).

在最终的亲核加成化合物2-F的芳香族区中的这些化学位移与9，10二氢-9-甲氧基-9-(4甲氧基苯基)-10-甲基吖啶的对应物是一致的，17b 这被证明是与过量的MeOH形成的9-苯基吖啶盐的加成化合物（支持信息中的图S7）。

In part one, the reactions of some active fluorine-containing compounds such as 2, 2-dihydropolyfluoroalkanoic acids and ethyl 2-hydropolyfluoroalkenoates were studied and various fluorine-containing heterocyclic compounds were synthesized. Using 2, 2-dihydropolyfluoroalkanoic acids as the starting material, 4-fluoroalkyl quinolin-2-ols, 2- [ -1-hydropolyfluoro-1-alkenyl] -4H-3, 1-benzoxazin-4-ones, 1-aryl -4, 9-dihydro-3-fluoro-alkyl-1H-pyrazo [3, 4-b] quinolin-4-ones, 5-fluoroalkyl-12H-quin olino [2, 1-b] quinazolin-12-ones, 4-fluoroalkyl-1, 3-dihydro-1, 5-benzodiazepin-2-ones and 4-fluoroalkyl-2H-pyrido [1, 2-a] pyrimidin-2-ones were synthesized through its condensation reaction with anilines, anthranilic acid, N'-aryl-o-aminobenzamides, o-nitro aniline, o-amino pyridine and their derivatives and the subsequent transformations. 5-Fluoroalkyl isoxazolidines, 3-fluoro-3-fluoroalkylisoxazolidino [4, 3-c] quinolin-4-ones, 3-fluoroalkylisoxazolino [4, 3-c] quinolin-4-ones and 2-aryl-3per fluoroacylindoles were synthesized by inter-and intramolecular 1, 3-dipolar cycloaddition of fluorine-containing olefins and nitrones.

第二部分，我们研究了α，α-二氟苄基卤类化合物的亚磺化脱卤反应、产物的转化及全氟烷基亚磺酸盐与芳环化合物的全氟烷基化反应，发现全氟苄基碘或溴及α，α一二氟苄基溴在保险粉等亚磺化脱卤试剂引发下可生成相应的亚磺酸盐；全氟苄基亚磺酸盐与氯气或溴反应可生成全氟苄基磺酰氯或磺酰溴；在烯烃存在下，全氟苄基碘则与烯烃发生加成反应，生成相应的1：1加成产物；在三价醋酸锰的作用下，部分芳香化合物如茴香醚，二甲氧基苯，吡啶，喹啉等可以和过量的全氟烷基亚磺酸盐发生双全氟烷基化反应，反应表现出一定的区域选择性，产率良好。

The chapter two was focused on the samarium diiodide promoted organic reactions and their applications in organic synthesis, firstly, a new synthesis of highly substituted cyclopentadienes from a,β-alkynone promoted by samarium diiodide was investigated and the highly substituted cyclopentadienes were prepared in moderate to good yields under mild conditions. Secondly, the Michael addition and Michael-aldol tandem reaction of diorganyl diselenides or diorganyl disulfides with α,β-alkynones mediated by samarium diiodide were studied and a series of alkenylsulfides and alkenylselenides were prepared in good yields. Then the highly regioselecfive nucleophilic addition of the allylsamarium bromide to α,β-alkynones were explored. We found that the allylsamarium bromide reacts with α,β-alkynones to afford regiospecificly 1. 2-nucleophilic addition products in good yields under mild condition. At last we studied the coupling reaction of aryl halides promoted by NiCl〓/PPh〓/Sm〓.

第二章 研究了二碘化钐、金属钐促进的有机反应：1、二碘化钐促进下α，β-炔基酮的偶联环化反应，提供了一种制备多取代环戊二烯的新方法；2、二碘化钐促进下的二硫醚、二硒醚与α，β-炔基酮的Michael加成反应，为高产率地制备多取代的烯基硫或烯基硒化合物提供了方便可靠的新方法；3、二碘化钐促进下的二硫醚、二硒醚与α，β-炔基酮和醛、酮的Michael—aldol串联反应，提供了一种一锅法高产率地制备多取代的含硫的烯丙基醇或含硒的烯丙基醇类化合物的方便可靠的原子经济性的新方法；4、烯丙基溴化钐与α，β-炔基酮的高度区域选择性的1，2-亲核加成反应；5、NiCl〓/PPh〓/Sm〓促进的卤代芳烃的偶联反应-一种从各种卤代芳烃制备联苯类化合物的有效方法。

This dissertation is mainly focused on the reactivity of methylenecyclopropanes and comprises six parts. 1 The reactions of methylenecyclopropanes with phenylsulfenyl chloride, phenylselenyl chloride and diphenyl diselenide; 2 The coupling reactions of the ring-opening products derivated from methylenecyclopropanes; 3 The palladium-catalyzed ring-enlargement of mono-aryl group substituted methylenecyclopropanes to cyclobutenes. 4 The gold-catalyzed domino ring-opening and ring-closing hydroamination of methylenecyclopropanes with sulfonamides; 5 The Lewis acid-catalyzed reactions of mono-aryl group substituted methylenecyclopropanes with diethyl ketomalonate in the presence of water; 6 The iodobenzene diacetate mediated novel 1,3-dipolar cycloaddition of methylenecyclopropanes, vinylidenecyclopropanes, and methylenecyclobutane with phthalhydrazine.

本论文主要研究了亚甲基环丙烷类化合物的一些化学反应性能，共由以下六部分组成：1、亚甲基环丙烷类化合物与苯硫氯、苯硒氯及二苯基二硒的反应；2、亚甲基环丙烷类化合物开环产物的偶联反应；3、单芳基取代的亚甲基环丙烷类化合物在钯催化剂作用下的扩环反应；4、金化合物催化磺酰胺对亚甲基环丙烷类化合物的串联开环关环氨氢化反应；5、路易斯酸催化亚甲基环丙烷类化合物与丙酮二羧酸二乙酯在有水存在下的反应；6、醋酸碘苯促进的亚甲基环丙烷类化合物、亚乙烯基环丙烷类化合物及亚甲基环丁烷类化合物与邻苯二甲酰肼的新型1，3-偶极环加成反应。

The dissertation mainly consists of two parts:1. The Reaction Chemistry of Alkynes under Palladium Catalysis Part 1 studies the reaction α,β-unsaturated carbonyl compounds with alkenylpalladium intermediate generated by nucleopalladation, and discovered 1 the Pd-catalyzed tandem addition reaction of halides, alkynes and α,β-unsaturated carbonyls,2 the four-component tandem addition reaction of halides, alkynes and α,β-unsaturated carbonyls, 3 the tandem intramolecular oxypalladation-conjugate additionreaction of alkynoic acids with α,β-enals. These new reactions provide notonly efficient highly stereoselective methods for the synthesis of γ,δ-unsaturated,polyunsaturated carbonyl compounds and γ-lactonic aldehydes, but also thebasic transformations for a number of C-C bond formation reactions which can be usedto design synthesis of many acyclic, cyclic or polycyclic compounds.

本论文的主要工作分为两个部分：一、钯催化下炔烃的反应化学在本小组前人工作的基础上，我们详细研究了炔烃亲核钯化产生的烯基钯中间体与α，β-不饱和羰基化合物的反应，发现两价钯催化下卤离子-炔烃-α，β-不饱和醛酮的串联加成反应、卤离子-炔烃-α，β-不饱和醛酮的西组分串联加成及炔酸分子内氧钯化-串联Michael型加成反应；由此发展了γ，δ-不饱和醛酮、多不饱和羰基化合物和带有醛酮基侧链的γ-丁内酯衍生物的高立体选择性合成方法，这一过量卤离子存在下的烯基钯对α，β-不饱和羰基化合物共轭加成反应的发现，为大量碳-碳键形成反应的实现提供了基础，使我们能够从这一基本反应出发，设计和开发多种分子内、分子间的碳碳成键反应，以好的立体、区域选择性组建开链、环状及多环类型的化合物。

For very long time, many research groups focus on using more than a stoichiometric amount of a chiral auxiliaries to obtain high enantioselectivity. There were mainly two sorts of processes reported on highly catalytic asymmetric addition of Grignard reagents to aldehydes. The former case was to transform Grignard reagent RMgX into other organometal reagents such as R_2Zn and R-Ti derivatives via complicated procedures at extremely low temperature. The later case was to link a chiral ligand to Mg in the form of organomagnesium amides or use chiral amine ligand catalyzing the alkylation of aldehydes.

格氏试剂对醛的不对称加成的报道大多需要大量的手性助剂以获得高的光学活性，而高度催化的格氏试剂对醛的不对称加成主要通过两种途径进行：一种是把格氏试剂转化成其他的有机金属试剂如R_2Zn和R-Ti化合物再对醛进行加成，反应通常在低温下进行；另一种是利用手性镁胺作为中间体或直接用手性胺催化来完成此反应。

First, when operating the DABCO-catalyzed Ireland-Claisen rearrangement of propargylic acrylates 18b-d, we added dienophiles 40a-f in the reaction system to capture the rearranged allenes products respectively. The Diels-Alder adducts 41a-i were obtained with complete regioselectivity. Thus a novel tandem Ireland-Claisen rearrangement /Diels-Alder reaction process with propargylic acrylates has been developed.

首先在进行DABCO-催化的丙烯酸炔丙酯类化合物18b-d的Ireland-Claisen重排反应的同时，于反应体系中分别加入亲二烯体40a-f捕获重排得到的连二烯中间体，一步反应获得了单一区域选择性的Diels-Alder环加成产物41a-i，从而创建了一条新颖的丙烯酸炔丙酯类化合物的Ireland-Claisen重排与Diels-Alder环加成的串联反应路线。

The largest chemical shifts were observed for the proton 1.48 ppm adjacent to the central pyridinium ring and para-protons 1.47 ppm with respect to the nitrogen of pyridinium.

在最终的亲核加成化合物2-F的芳香族区中的这些化学位移与9，10二氢-9-甲氧基-9-(4甲氧基苯基)-10-甲基吖啶的对应物是一致的，17b 这被证明是与过量的MeOH形成的9-苯基吖啶盐的加成化合物（支持信息中的图S7）。

Learn addition of double bond with various halide, including electrophilic addition and free-radical addition.

了解各种含卤素化合物对碳碳双键的加成，包括亲电加成和自由基加成。

Copper iodide CuI has a apparent inhibition effect on addition rearrange of the Grignard reagent with carbonyl compounds.

为抑制烯丙基格氏试剂与羰基化合物加成反应中的重排反应，进行了碘化亚铜CuI对此类格氏试剂及加成产物组分比例关系的研究，CuI对这类化合物加成反应重排有明显的抑制作用。

Neither the killing of Mr Zarqawi nor any breakthrough on the political front will stop the insurgency and the fratricidal murders in their tracks.

在对危险的南部地区访问时，他斥责什叶派民兵领导人对中央集权的挑衅行为。

In fact,I've got him on the satellite mobile right now.

实际上 我们已接通卫星可视电话了