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1.
Pengjin Qin Li-An Wang Prof. Joseph M. O'Connor Prof. Kim K. Baldridge Yifan Li Burak Tufekci Jiyue Chen Prof. Arnold L. Rheingold 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(41):18114-18121
Triene 6π electrocyclization, wherein a conjugated triene undergoes a concerted stereospecific cycloisomerization to a cyclohexadiene, is a reaction of great historical and practical significance. In order to circumvent limitations imposed by the normally harsh reaction conditions, chemists have long sought to develop catalytic variants based upon the activating power of metal–alkene coordination. Herein, we demonstrate the first successful implementation of such a strategy by utilizing [(C5H5)Ru(NCMe)3]PF6 as a precatalyst for the disrotatory 6π electrocyclization of highly substituted trienes that are resistant to thermal cyclization. Mechanistic and computational studies implicate hexahapto transition-metal coordination as responsible for lowering the energetic barrier to ring closure. This work establishes a foundation for the development of new catalysts for stereoselective electrocyclizations. 相似文献
2.
Donald Craig 《Tetrahedron: Asymmetry》1991,2(12):1177-1180
The synthesis and thermally-induced intramolecular Diels-Alder (IMDA) reaction of (S)s-(+)-S-[(1E,7E)-1,7,9-decatrienyl]-S-phenyl-N-(p-tolylsulphonyl)sulphoximine 4 is described. A model is proposed for the cis-selectivity of the cycloaddition based on previous results from the reactions of sulphonyl-substituted trienes. The stereochemistry of the major cis-fused cycloadduct is determined by single-crystal X-ray analysis of that obtained from reaction of racemic 4. 相似文献
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4.
The reaction of gaseous H2S with aqueous ammonium heptamolybdate in the presence of triethylenetetramine (trien) gave a red complex. The complex was recrystallized in hot water and characterized by element analysis and UV, visible, IR, and 1H NMR spectroscopy. PMR has revealed accidental magnetic equivalence, resulting from the proximity of [MoS4]2- species in one complex molecule to the open triethylenetetramine ligand of another molecule. (TrienH2)[MoS4] crystallizes in the orthorhombic crystal system, space group Pca21, a=13.045(2), b=16.461(3), c=13.754(2) , =90, =90, =90°, V=2953.5(9) 3, Z=8, R1=0.0323, wR2=0.0730. The structure consists of the tetrahedral tetrathiomolybdate anions, forming an extended 3D framework in solids due to the interactions with triene cations via Mo-S...H-N hydrogen bonds. 相似文献
5.
Pengjin Qin Li‐An Wang Joseph M. O'Connor Kim K. Baldridge Yifan Li Burak Tufekci Jiyue Chen Arnold L. Rheingold 《Angewandte Chemie (International ed. in English)》2020,59(41):17958-17965
Triene 6π electrocyclization, wherein a conjugated triene undergoes a concerted stereospecific cycloisomerization to a cyclohexadiene, is a reaction of great historical and practical significance. In order to circumvent limitations imposed by the normally harsh reaction conditions, chemists have long sought to develop catalytic variants based upon the activating power of metal–alkene coordination. Herein, we demonstrate the first successful implementation of such a strategy by utilizing [(C5H5)Ru(NCMe)3]PF6 as a precatalyst for the disrotatory 6π electrocyclization of highly substituted trienes that are resistant to thermal cyclization. Mechanistic and computational studies implicate hexahapto transition‐metal coordination as responsible for lowering the energetic barrier to ring closure. This work establishes a foundation for the development of new catalysts for stereoselective electrocyclizations. 相似文献
6.
E. I. Klimova M. Martinez Garcia T. Klimova L. Ruiz Ramirez J. M. Mendez Stivalet N. N. Meleshonkova 《Russian Chemical Bulletin》2000,49(3):514-519
3,5-Bis(ferrocenylmethylene)-1-methyl-4-methylenepiperidine, a diferrocenyltriene with a fixeds-cisoid conformation of the exocyclic double bonds, was synthesized. On heating, this compound cyclodimerizes according to
the [4+2]-cycloaddition scheme; it forms Diels-Alder adducts with azodicarboxylic and maleic acidN-phenylimides. The compound easily cyclodimerizes in the presence of acids by a proton cyclodimerization mechanism to give
a spiro cyclodimer. The triene also adds a 3,5-bis(ferrocenylmethylene)-1,4-dimethyl-1-azonia-4-cyclohexyl salt to the terminal
methylene group yielding linear and cyclic addition products.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 511–516, March, 2000. 相似文献
7.
Bo Huang Zhen‐Yuan Huang Chao‐Jiang Xiao Xiang Dong Bei Jiang 《Helvetica chimica acta》2015,98(4):527-533
Three new phenolic tricyclic diterpenoids, including two sempervirane diterpenoids, hispidanols A and B ( 1 and 2 , resp.), and one totarane diterpenoid, totara‐8,11,13‐triene‐13→16‐hemiacetal ( 3 ), along with 14 known compounds, 4 – 17 , were isolated from the AcOEt‐soluble fraction of the 70%‐acetone extract of rhizomes of Isodon hispida. Their structures were elucidated based on the analyses of extensive spectroscopic data and physicochemical properties. 相似文献
8.
碳碳双键是有机化学中最基本的官能团之一 ,在众多构筑碳碳双键的方法中Ramberg B cklund反应占有很重要的地位 .该方法的关键步骤是α 卤代砜在碱性条件下 ,发生 1,3 消除反应 ,得到环状砜 ,然后重排失去SO2 形成双键 ,这样形成的双键位置确定 ,即具有良好的区域选择性 ,并且在不同的反应条件下可得到不同构型的产物 ,因而在有机合成中有很好的应用前景 .对Ramberg B cklund反应进行了较为详细的综述 ,并对我们实验室所进行的反应条件的改进和优化以及目前的研究进展作了总结 . 相似文献
9.
Yuhang Zhu Yilei Liao Shuqi Jin Liyuan Ding Prof. Dr. Guofu Zhong Prof. Dr. Jian Zhang 《Chemical record (New York, N.Y.)》2023,23(5):e202300012
Aryl alkenes represents one of the most widely occurring structural motif in countless drugs and natural products, and direct C−H functionalization of aryl alkenes provides atom- step efficient access toward valuable analogues. Among them, group-directed selective olefinic α- and β-C−H functionalization, bearing a directing group on the aromatic ring, has attracted remarkable attentions, including alkynylation, alkenylation, amino-carbonylation, cyanation, domino cyclization and so on. These transformations proceed by endo- and exo−C−H cyclometallation and provide aryl alkene derivatives in excellent site- stereo-selectivity. Enantio-selective α- and β- olefinic C−H functionalization were also covered to synthesis axially chiral styrenes. 相似文献
10.
Hong Mei Qu Xin Hui Niu Juan Li Jun Liu Li Li Jiang Jian Ke Tang Li Shan Zhou 《中国化学快报》2012,23(10):1137-1140
The linear trienes were obtained in high yields by copper-mediated cycloaddition of 2,5-bis(trimethylsilyl)zirconacyclopentadienes with dimethyl acetylenedicarboxylate(DMAD) which can be quantitatively converted to novel asymmetric hexasubstituted cyclohexadienes with high(E)-stereoselectivity.The structure of cyclohexadienes was determined via X-ray analysis. 相似文献