锡促进的烯丙基硒醚和烯丙基硫醚的合成

在金属锡促进下，烯丙基溴与二硒醚或二硫醚反应，生成烯丙基硒醚或烯丙基硫醚 。     

铟促进的烯丙基硒醚的合成

烯丙基溴和炔丙基溴在铟促进下与二硒化合物反应，生成烯丙基和炔丙基硒醚。反应无需严格的无水无氧条件，烯丙基溴以α-位与二硒化合物反应，产率55%～91%。     

合成烯丙基芳基硒醚的一种简便方法——烯丙基锌与二芳基二硒醚反应

烯丙基溴与锌粉在0～10 ℃下THF中反应生成烯丙基锌，后者与二芳基二硒醚 在THF中、室温下反应生成烯丙基芳基硒醚，产率63%～75%。     

电化学促进的N-烯丙基硫代酰胺的硒化/环化合成2-噻唑啉（英文）

建立了一种电化学促进N-烯丙基硫代酰胺的串联硒化/环化新方法,用来制备含硒官能团的2-噻唑啉衍生物.该方法反应条件温和,底物范围广.初步的机理研究表明,反应过程中有硒自由基的参与.该方法操作简单且无需使用催化剂、过渡金属和氧化剂.     

有机硒试剂在有机合成中应用的新进展

近代硒元素有机化学诞生于1973年,有机硒试剂在合成化学上应用已涉及于碳碳双键生成,烯丙基硒氧化物[2、3]西格马重排和环官能化等方面,特别在天然产物和生物活性药用物质合成中应用颇广。     

希土烯丙基化合物的研究──X．钆、钬、铒、镱和镥的2－甲基烯丙基四氢呋喃配合物的合成研究

希土烯丙基化合物的研究──Ｘ．钆、钬、铒、镱和镥的２－甲基烯丙基四氢呋喃配合物的合成研究庄善明，黄祖恩，高云（复旦大学化学系，上海２００４３３）关键词希土，２－甲基烯丙基，四氢呋喃，配合物，合成人们对个过渡金属的烯丙基化合物进行了较深人的研究，它们在...     

七—（2，3，6，—0—烯丙基）—β—环糊精的合成与表征

利用氢氧化钠作催化剂使β-环糊精(简称β-CD)被烯丙基修饰合成了七-(2，3，6-O-烯丙基)-β-环糊精[Heptakis-(2,3,6-O-allyl)-β-CD]。用正交实验法考察了反应温度、反应时间、催化剂用量和修饰剂-烯丙基溴用量等因素对合成目标化合物的影响，得出合成七-(2，3，6-O烯丙基)-β-环糊精的最佳实验条件：n(β-环糊精)：n(烯丙基溴)＝1：86．92，n(催化剂):n(烯丙基溴)＝1：1．052。产物经元素分析，IR和1HNMR表征和确认。     

烯丙基碘和锡与醛的选择加成反应

含活性基团的醛可与烯丙碘和锡粉直接进行亲核加成反应，得到高烯丙基的醇，水的存在不利于此反应的进行，与烯丙基溴相比，烯丙基碘反应活性更强，可在短时间内得较高的产率。     

催化合成烯丙基紫罗兰酮─—紫罗兰酮研究（V）

本文报道了以烯丙基丙酮和从山苍子油单离纯化所获柠檬醛为主要起始物，在催化剂作用下，合成假性烯内基紫罗兰酮，最终获得目标产物烯丙基紫罗兰酮，结果满意。假性烯丙基紫罗兰酮收率达７４．５％，目标产物烯内基紫罗兰酮收率达８７．５％。     

水相中磷钼酸催化三组分合成烯丙基胺

以磷钼酸作为催化剂，芳香醛、胺和三丁基烯丙基锡三组分在水作为溶剂，室温下高产率的得到相应的烯丙基胺。     

Solvent-induced allylic rearrangements in poly(trichlorobutadiene) chains

It was established by Fourier-transform IR and¹H NMR spectroscopy that a portion of the units of poly(1,1,2- and 1,2,3-trichlorobuta-1,3-diene) chains rearrange with migration of the allylic chlorine (1–4%) and allylic hydrogen (3–10%) under the influence of chloroform. Rearrangement with the migration of hydrogen under the influence of CDCl₃, CCl₄, and THF was also observed. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 763–768, April, 1997.     

Highly selective palladium catalyzed kinetic resolution and enantioselective substitution of racemic allylic carbonates with sulfur nucleophiles: asymmetric synthesis of allylic sulfides,allylic sulfones,and allylic alcohols

We describe the highly selective palladium catalyzed kinetic resolutions of the racemic cyclic allylic carbonates rac-1 a-c and racemic acyclic allylic carbonates rac-3 aa and rac-3 ba through reaction with tert-butylsulfinate, tolylsulfinate, phenylsulfinate anions and 2-pyrimidinethiol by using N,N'-(1R,2R)-1,2-cyclohexanediylbis[2-(diphenylphosphino)-benzamide] (BPA) as ligand. Selectivities are expressed in yields and ee values of recovered substrate and product and in selectivity factors S. The reaction of the cyclohexenyl carbonate 1 a (>/=99 % ee) with 2-pyrimidinethiol in the presence of BPA was shown to exhibit, under the conditions used, an overall pseudo-zero order kinetics in regard to the allylic substrate. Also described are the highly selective palladium catalyzed asymmetric syntheses of the cyclic and acyclic allylic tert-butylsulfones 2 aa, 2 b, 2 c, 2 d and 4 a-c, respectively, and of the cyclic and acyclic allylic 2-pyrimidyl-, 2-pyridyl-, and 4-chlorophenylsulfides 5 aa, 5 b, 5 ab, 6 aa-ac, 6 ba and 6 bb, respectively, from the corresponding racemic carbonates and sulfinate anions and thiols, respectively, in the presence of BPA. Synthesis of the E-configured allylic sulfides 6 aa, 6 ab, 6 ac and 6 bb was accompanied by the formation of minor amounts of the corresponding Z isomers. The analogous synthesis of allylic tert-butylsulfides from allylic carbonates and tert-butylthiol by using BPA could not be achieved. Reaction of the cyclopentenyl esters rac-1 da and rac-1 db with 2-pyrimidinethiol gave the allylic sulfide 5 c having only a low ee value. Similar results were obtained in the case of the reaction of the cyclohexenyl carbonate rac-1 a and of the acyclic carbonates rac-3 aa and rac-3 ba with 2-pyridinethiol and lead to the formation of the sulfides 5 ab, 6 ab, and 6 bb, respectively. The low ee values may be ascribed to the operating of a "memory effect", that is, both enantiomers of the substrate give the substitution product with different enantioselectivities. However, in the reaction of the racemic carbonate rac-1 a as well as of the highly enriched enantiomers 1 a (>/=99 % ee) and ent-1 a (>/=99 % ee) with 2-pyrimidinethiol the ee values of the substrates and the substitution product remained constant until complete conversion. Similar results were obtained in the reaction of the cyclic carbonates rac-1 a, ent-1 a (>/=99 % ee) and ent-1 c (>/=99 % ee) with lithium tert-butylsulfinate. Thus, in the case of rac-1 a and 2-pyrimidinthiol and tert-butylsulfinate anion as nucleophiles the enantioselectivity of the substitution step is, under the conditions used, independent of the chirality of the substrate; this shows that no "memory effect" is operating in this case. Hydrolysis of the carbonates ent-1 a-c, ent-3 aa and ent-3 ba, which were obtained through kinetic resolution, afforded the enantiomerically highly enriched cyclic allylic alcohols 9 a-c (>/=99 % ee) and acyclic allylic alcohols 10 a (>/=99 % ee) and 10 b (99 % ee), respectively.     

Ultrasound-accelerated synthesis of chiral allylic alcohols promoted by indium metal

The 2-iodomethyl-O-isopropylidine acetals undergo smoothly β-elimination by indium metal in methanol under sonication to afford the corresponding allylic alcohols in excellent yields with high selectivity. This method tolerates both acid and base labile functional and protecting groups and also free hydroxyl groups present in the molecule. Improved yields and enhanced rates are the remarkable features obtained by ultrasound.     

Ruthenium-catalyzed synthesis of allylic alcohols: boronic acid as a hydroxide source

Secondary allylic alcohols were synthesized from linear allylic halides or carbonates using a catalytic amount of a ruthenium complex in the presence of boronic acid. The effects of solvent, base, ruthenium precursor, and boronic acid were fully explored, and the scope of the reaction was extended to various substrates. We also describe a preliminary investigation towards an enantioselective process.