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91.
The transformation of C? H bonds into other chemical bonds is of great significance in synthetic chemistry. C? H bond‐activation processes provide a straightforward and atom‐economic strategy for the construction of complex structures; as such, they have attracted widespread interest over the past decade. As a prevalent directing group in the field of C? H activation, the amide group not only offers excellent regiodirecting ability, but is also a potential C? N bond precursor. As a consequence, a variety of nitrogen‐containing heterocycles have been obtained by using these reactions. This Focus Review addresses the recent research into the amide‐directed tandem C? C/C? N bond‐formation process through C? H activation. The large body of research in this field over the past three years has established it as one of the most‐important topics in organic chemistry. 相似文献
92.
93.
A Unified Strategy to 6–5–6–5–6‐Membered Epipolythiodiketopiperazines: Studies towards the Total Synthesis of Scabrosin Diacetate and Haematocin
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Hannes F. Zipfel Prof. Dr. Erick M. Carreira 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(35):12475-12480
The family of epipolythiodiketopiperazine (ETP) natural products consists of over 200 members possessing a wide diversity of structures and biological activity. Recently, the subgroup of 6–5–6–5–6‐membered ETPs has gained substantial attention, which has resulted in several total syntheses. Despite all the efforts that have been invested into accessing these complex structures, no synthesis of scabrosin diacetate ( 1 a ) and its related esters has been reported. Herein, our attempts towards scabrosin diacetate ( 1 a ) and haematocin ( 3 ) starting from diketopiperazine 12 a as a late‐stage intermediate are presented. Diketopiperazine 12 a can be conveniently accessed in multigram quantities from aldehyde 18 and diketopiperazine 21 and was envisioned to serve as a general platform for the synthesis of 6–5–6–5–6‐membered ETPs. 相似文献
94.
Valentyn Rudzevich Dr. Oleg Kasyan Dr. Andriy Drapailo Dr. Michael Bolte Dr. Dieter Schollmeyer Dr. Volker Böhmer Dr. 《化学:亚洲杂志》2010,5(6):1347-1355
Thiacalix[4]arene 2 , calix[4]arene 3 a and its tetraether fixed in the cone conformation 3 b form homo‐ and heterodimeric capsules in apolar solvents, which are held together by a seam of NH???O=P hydrogen bonds between carbamoylmethyl phospine oxide functions attached to their wide rim. Their internal volume of ~370 Å3 requires the inclusion of a suitable guest. Although neutral molecules such as adamantane (derivatives) or tetraethylammonium cations form kinetically stable complexes (1H‐ and 31P‐time scale), the included solvent is rapidly exchanged. The internal mobility of the included tetraethylammonium cation is distinctly higher (ΔG=42.5 and 49.7 kJ mol?1 for 3 a and 3 b ) than that for similar capsules of tetraurea calix[4]arenes 1 . Mixtures of 1 with 2 , 3 a , or 3 b contain only the two homodimers but the heterodimerization occurs with the tetraloop tetraurea 6 , which cannot form homodimers. Two dimers with cationic guests ( 2? (C5H5)2Co+ ?2 and 3 a? Et3NH+ ? H2O ?3 a ) were confirmed by single‐crystal X‐ray analysis. 相似文献
95.
Ring Opening Metathesis Polymerization of Bicyclic α,β‐Unsaturated Anhydrides for Ready‐to‐be‐grafted Polymers Having Tailored pH‐Responsive Degradability
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Heejin Kim Sungwhan Kim Sunyoung Kang Youngjun Song Dr. Suyong Shin Dr. Seonju Lee Minji Kang Dr. So Hee Nam Prof. Dr. Yan Lee 《Angewandte Chemie (International ed. in English)》2018,57(38):12468-12472
Polymers having α,β‐unsaturated anhydrides as repeating units were synthesized by ring opening metathesis polymerization (ROMP). The anhydride moieties were ready‐to‐be‐grafted with amines to form acid‐labile cis‐α,β‐unsaturated acid amide linkages. The pH‐responsive reversible de‐grafting can be controlled by changing the intramolecular accessibility between acid and amide groups. The alendronate‐grafted ROMP polymers showed distinct pH‐dependent cytotoxicity according to the anhydride structures. 相似文献
96.
A. V. Tarasov P. O. Yablonsky Yu. A. Moskvichev 《Chemistry of Heterocyclic Compounds》2003,39(1):119-122
Various methods were studied for the oxidation of 2-methyl-5-(phenylsulfonyl)benzenesulfamide and its derivatives. The oxidation by sodium dichromate in sulfuric acid was found most efficient. The effects of temperature, concentration, reagent ratio, and time of the oxidation reaction on the yield of the desired product were investigated. Conditions were proposed for obtaining the desired product in yields up to 95%. A synthesis was developed for a series of new saccharin derivatives. 相似文献
97.
Zhang M Imm S Bähn S Neubert L Neumann H Beller M 《Angewandte Chemie (International ed. in English)》2012,51(16):3905-3909
Amid(e) them all: primary carboxamides and ureas react with aromatic and aliphatic amines in the presence of a copper catalyst to give a wide range of functionalized amides. 相似文献
98.
99.
The osmotic coefficients of acetamide, propionamide and butyramide in water were measured at 293.15, 298.15 and 308.15 K using
the isopiestic method. The activity coefficients were calculated for the aliphatic amides and the pairwise free energy coefficients
for solute-solute interactions were determined according to the McMillan-Mayer theory. The osmotic and activity coefficients
of amides are discussed in terms of solute-solute interactions. 相似文献
100.
Dr. Yasuhiro Yamashita Takaki Imaizumi Dr. Xun‐Xiang Guo Prof. Dr. Shū Kobayashi 《化学:亚洲杂志》2011,6(9):2550-2559
Asymmetric [3+2] cycloaddition of α‐aminoester Schiff bases with substituted olefins is one of the most efficient methods for the preparation of chiral pyrrolidine derivatives in optically pure form. In spite of its potential utility, applicable substrates for this method have been limited to Schiff bases that bear relatively acidic α‐hydrogen atoms. Here we report a chiral silver amide complex for asymmetric [3+2] cycloaddition reactions. A silver complex prepared from silver bis(trimethylsilyl)amide (AgHMDS) and (R)‐DTBM‐SEGPHOS worked well in asymmetric [3+2] cycloaddition reactions of α‐aminoester Schiff bases with several olefins to afford the corresponding pyrrolidine derivatives in high yields with remarkable exo‐ and enantioselectivities. Furthermore, α‐aminophosphonate Schiff bases, which have less acidic α‐hydrogen atoms, also reacted with olefins with high exo‐ and enantioselectivities. The stereoselectivities of the [3+2] cycloadditions with maleate and fumarate suggested that the reaction proceeded by means of a concerted mechanism. An NMR spectroscopic study indicated that complexation of AgHMDS with the bisphosphine ligand was not complete, and that free AgHMDS, which did not show any significant catalytic activity, existed in the catalyst solution. This means that significant ligand acceleration occurred in the current reaction system. 相似文献