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11.
Oxidative Cross‐Coupling of Allenyl Ketones and Organoboronic Acids: Expeditious Synthesis of Highly Substituted Furans 下载免费PDF全文
Ying Xia Dr. Yamu Xia Rui Ge Zhen Liu Dr. Qing Xiao Dr. Yan Zhang Prof. Dr. Jianbo Wang 《Angewandte Chemie (International ed. in English)》2014,53(15):3917-3921
Allenyl ketones are employed as coupling partners in palladium‐catalyzed oxidative cross‐coupling reactions with organoboronic acids. This reaction constitutes an efficient methodology for the synthesis of highly substituted furan derivatives. Palladium‐carbene migratory insertion is proposed as the key step in this transformation. 相似文献
12.
Lin Yang Guoli He Ruifeng Yin Dr. Lili Zhu Prof. Dr. Xiaoxia Wang Prof. Dr. Ran Hong 《Angewandte Chemie (International ed. in English)》2014,53(43):11600-11604
Polyketide antibiotics bearing skipped polyols represent a synthetic challenge. A SiCl4‐promoted oxonia‐Cope rearrangement of syn,syn‐2‐vinyl‐1,3‐diols was developed to forge an array of 1,5‐pentenediols, thus providing versatile motifs for the preparation of 1,2,3,5‐stereoarrays in a highly stereoselective manner. Further exploration with Sn(OTf)2 realized the rearrangement of a cross‐aldehyde which tactically warrants the utility of the current approach to access complex polyketides. The origin of high stereoselectivity is attributed to a chairlike anti‐conformation of the oxonium ion intermediate. 相似文献
13.
Yuki Kataoka Dr. Naoya Kanbayashi Naoka Fujii Dr. Taka-aki Okamura Prof. Takeharu Haino Prof. Kiyotaka Onitsuka 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(26):10372-10377
π-Stacked polymers, which consist of layered π-electron systems in a polymer, can be expected to be used in molecular electronic devices. However, the construction of a stable π-stacked structure in a polymer is considerably challenging because it requires sophisticated designs and precise synthetic methods. Herein, we present a novel π-stacked architecture based on poly(quinolylene-2,3-methylene) bearing alanine derivatives as the side chain, obtained through the living cyclo-copolymerization of an o-allenylaryl isocyanide. In the resulting polymer, the neighboring quinoline rings of the main chain form a layered structure with π–π interactions, which is stabilized by intramolecular hydrogen bonds. The vicinal quinoline units form two independent helices and the whole molecule is a twisted-tape structure. This structure is established on the basis of UV/CD spectra, theoretical calculations, and atomic-force microscopy. 相似文献
14.
Yuki Kataoka Naoya Kanbayashi Naoka Fujii Taka‐aki Okamura Takeharu Haino Kiyotaka Onitsuka 《Angewandte Chemie (International ed. in English)》2020,59(26):10286-10291
π‐Stacked polymers, which consist of layered π‐electron systems in a polymer, can be expected to be used in molecular electronic devices. However, the construction of a stable π‐stacked structure in a polymer is considerably challenging because it requires sophisticated designs and precise synthetic methods. Herein, we present a novel π‐stacked architecture based on poly(quinolylene‐2,3‐methylene) bearing alanine derivatives as the side chain, obtained through the living cyclo‐copolymerization of an o‐allenylaryl isocyanide. In the resulting polymer, the neighboring quinoline rings of the main chain form a layered structure with π–π interactions, which is stabilized by intramolecular hydrogen bonds. The vicinal quinoline units form two independent helices and the whole molecule is a twisted‐tape structure. This structure is established on the basis of UV/CD spectra, theoretical calculations, and atomic‐force microscopy. 相似文献
15.
Manuel Plaza Christian Jandl Thorsten Bach 《Angewandte Chemie (International ed. in English)》2020,59(31):12785-12788
Trisubstituted allenes with a 3‐(1′‐alkenylidene)‐pyrrolidin‐2‐one motif were successfully deracemized (13 examples, 86–98 % ee) employing visible light (λ=420 nm) and a chiral triplet sensitizer as the catalyst (2.5 mol %). The photocatalyst likely operates by selective recognition of one allene enantiomer via hydrogen bonds and by a triplet‐sensitized racemization process. Even a tetrasubstituted allene (45 % ee) and a seven‐membered 3‐(1′‐alkenylidene)‐azepan‐2‐one (62 % ee) could be enantiomerically enriched under the chosen conditions. It was shown that the axial chirality of the allenes can be converted into point chirality by a Diels–Alder (94–97 % ee) or a bromination reaction (91 % ee). Ring opening of the five‐membered pyrrolidin‐2‐one was achieved without significantly compromising the integrity of the chirality axis (92 % ee). 相似文献
16.
Stephen Brown Ronald Grigg Joanne Hinsley Stewart Korn Visuvanathar Sridharan Michael D. Uttley 《Tetrahedron》2001,57(52):809-10355
A wide variety of aryl/heteroaryl iodides undergo an intermolecular Heck reaction with alkylallenes to furnish 1,3-dienes. These subsequently react in situ with various dienophiles to give Diels–Alder adducts. The chemistry has been extended to incorporate cyclisation-anion capture methodology and the stereochemistry of the products has been determined. 相似文献
17.
18.
Dr. Xiaodan Chen Dr. Zhongshu Li Prof. Dr. Gernot Frenking Prof. Dr. Israel Fernández Prof. Lili Zhao Prof. Dr. Hansjörg Grützmacher 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(33):7912-7920
Phosphaheteroallenes R−P=C=L, with L = N-heterocyclic carbenes (NHCs), can be viewed to a certain extent as phosphaisonitriles stabilized with NHCs, R−P=C:←L. The suitability of these molecules as ligands for coinage-metal ions was investigated and coordination through the central carbon center was observed in most cases. A combination of experiments, spectroscopic methods, and DFT calculations indicates the presence of a hidden electron pair at the carbon center of R−P=C:←L. Remarkably, this lone pair also inserts intramolecularly in C−H bonds showing the carbene-type reactivity which is expected for phosphaisonitriles. 相似文献
19.
Samir Z. Zard 《Helvetica chimica acta》2019,102(8)
The present account discusses in detail various mechanistic features of the degenerative radical addition‐transfer of xanthates and related thiocarbonylthio congeners and makes a comparison with the more classical Kharasch reactions to which it is similar in certain aspects. The xanthate group reacts reversibly with the ‘active’ radicals in the medium and is able to store them in a somewhat inactive form. This increases their effective lifetime in the medium and, at the same time, lowers their absolute concentration while regulating their relative concentration. These properties translate into a powerful carbon–carbon bond forming process, especially as regards intermolecular additions to electronically unbiased (‘unactivated’) alkenes. Most functional groups are tolerated, in particular polar functions that often require protection with other chemistries. This broad versatility is illustrated by examples where the xanthate addition to the alkene is combined with other, more classical reactions to provide a convergent, rapid access to a wide range of useful structures. Emphasis has been placed on the synthesis of open chain and more complex carbocycles, as well as on the transfer of chirality. These ‘radical alliances’ include organosilicon chemistry, the Diels–Alder cycloaddition and cheletropic extrusion of sulfur dioxide, the Claisen sigmatropic rearrangement, and the Horner–Wadsworth–Emmons (HWE) condensation. 相似文献
20.
Dr. Carlos Lázaro-Milla Jon Macicior Dr. Hikaru Yanai Prof. Dr. Pedro Almendros 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(41):8983-8989
Herein, we report investigations embodying the first example of reversal of the native regioselectivity in the reaction of allenols with electrophiles. The effortlessness of C−C bond formation, mild reaction conditions, neither catalysts nor light irradiation, and exquisite selectivity, both in terms of functional-group tolerance and chemo-, site-, and stereo-selectivity, converts this trifluorosulfonylation-rearrangement sequence into an appealing protocol for the preparation of novel functionalized enones. The synthetic utility of this method has been validated by the conversion of the initially prepared bis(triflyl)enones into a variety of bis(triflyl)-functionalized molecules such as 1,3-dienes, allylic alcohols, pyrroles, pyrazoles, and chromenes. Besides, DFT calculations have provided a reliable understanding of observed selectivity. 相似文献