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31.
Lewis Acid Catalyzed Condensation–Cyclization Cascade: Direct Synthesis of Di/Trifluoromethyl‐1,2,3,4‐tetrahydroquinazolines 下载免费PDF全文
Prof. Dr. G. K. Surya Prakash Dr. Attila Papp Socrates B. Munoz Nathan May John‐Paul Jones Prof. Dr. Ralf Haiges Prof. Dr. Pierre Mothé Esteves Dr. Thomas Mathew 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(28):10170-10178
Condensed heterocycles such as quinazolines constitute the framework of many promising drugs. The great impact of the dramatic fluorine effect in pharmaceuticals prompted a great surge in the quest for fluorinated drug design resulting in over 20 % fluorine‐containing drugs in the market today. Therefore, finding an efficient and cost‐effective method for the direct synthesis of fluorine‐tagged quinazoline systems is of great significance in the pharmaceutical arena. For the first time, a one‐pot sequential condensation–cyclization reaction to form selectively the difluoro/trifluoromethylated tetrahydroquinazolines from simple components difluoro/trifluoroacetaldehyde hemiacetal and aromatic amines is reported. Our recent studies using difluoro/trifluoroacetaldehyde hemiacetal as simple and elegant difluoro/trifluoromethyl synthons and metal triflates such as gallium triflate as safe and stable Lewis acid catalysts led us to this direct synthesis protocol for the expedient and convenient synthesis of fluorinated quinazolines. DFT calculations at PCM/B3LYP/6‐31++G** were carried out for evaluating a possible reaction mechanism for this cyclization. According to the DFT calculations, product stereochemistry is thermodynamically driven, favoring the cis isomer as the major product, which is also confirmed experimentally. 相似文献
32.
A Highly Effective Ruthenium System for the Catalyzed Dehydrogenative Cyclization of Amine–Boranes to Cyclic Boranes under Mild Conditions 下载免费PDF全文
Dr. Christopher J. Wallis Dr. Gilles Alcaraz Dr. Alban S. Petit Dr. Amalia I. Poblador‐Bahamonde Dr. Eric Clot Dr. Christian Bijani Dr. Laure Vendier Dr. Sylviane Sabo‐Etienne 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(37):13080-13090
We recently disclosed a new ruthenium‐catalyzed dehydrogenative cyclization process (CDC) of diamine–monoboranes leading to cyclic diaminoboranes. In the present study, the CDC reaction has been successfully extended to a larger number of diamine–monoboranes ( 4 – 7 ) and to one amine–borane alcohol precursor ( 8 ). The corresponding NB(H)N‐ and NB(H)O‐containing cyclic diaminoboranes ( 12 – 15 ) and oxazaborolidine ( 16 ) were obtained in good to high yields. Multiple substitution patterns on the starting amine–borane substrates were evaluated and the reaction was also performed with chiral substrates. Efforts have been spent to understand the mechanism of the ruthenium CDC process. In addition to a computational approach, a strategy enabling the kinetic discrimination on successive events of the catalytic process leading to the formation of the NB(H)N linkage was performed on the six‐carbon chain diamine–monoborane 21 and completed with a 15N NMR study. The long‐life bis‐σ‐borane ruthenium intermediate 23 possessing a reactive NHMe ending was characterized in situ and proved to catalyze the dehydrogenative cyclization of 1 , ascertaining that bis σ‐borane ruthenium complexes are key intermediates in the CDC process. 相似文献
33.
Sustainable Synthesis of Chiral Tetrahydrofurans through the Selective Dehydration of Pentoses 下载免费PDF全文
Robert W. Foster Dr. Christopher J. Tame Dr. Dejan‐Krešimir Bučar Prof. Helen C. Hailes Dr. Tom D. Sheppard 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(45):15947-15950
L ‐Arabinose is an abundant resource available as a waste product of the sugar beet industry. Through use of a hydrazone‐based strategy, L ‐arabinose was selectively dehydrated to form a chiral tetrahydrofuran on a multi‐gram scale without the need for protecting groups. This approach was extended to other biomass‐derived reducing sugars and the mechanism of the key cyclization investigated. This methodology was applied to the synthesis of a range of functionalized chiral tetrahydrofurans, as well as a formal synthesis of 3R‐3‐hydroxymuscarine. 相似文献
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Dr. Pilar Ventosa‐Andrés Dr. Agustina La‐Venia Dr. Carlos Alfonso Barea Ripoll Dr. Ludmila Hradilová Dr. Viktor Krchňák 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(37):13112-13119
Herein, we describe the synthesis of molecular scaffolds consisting of medium‐sized fused heterocycles using amino acids, which are some of the most useful building blocks used by nature as well as chemists to create structural diversity. The acyclic precursors were assembled by using traditional Merrifield solid‐phase peptide synthesis, and cyclization was carried out through acid‐mediated tandem endocyclic N‐acyliminium ion formation, followed by nucleophilic addition with internal nucleophiles. The synthesis of molecular scaffolds consisting of seven‐, eight‐, and nine‐membered rings proceeded with full stereocontrol of the newly generated stereogenic center in most cases. 相似文献
37.
Functionalization of Intramolecular Frustrated Lewis Pairs by 1,1‐Carboboration with Conjugated Enynes 下载免费PDF全文
Dr. Andreas Feldmann Dr. Gerald Kehr Dr. Constantin G. Daniliuc Dr. Christian Mück‐Lichtenfeld Prof. Dr. Gerhard Erker 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(35):12456-12464
The vicinal P/B frustrated Lewis pair (FLP) Mes2PCH2CH2B(C6F5)2 undergoes 1,1‐carboboration reactions with the Me3Si‐substituted enynes to give ring‐enlarged functionalized C3‐bridged P/B FLPs. These serve as active FLPs in the activation of dihydrogen to give the respective zwitterionic [P]H+/[B]H? products. One such product shows activity as a metal‐free catalyst for the hydrogenation of enamines or a bulky imine. The ring‐enlarged FLPs contain dienylborane functionalities that undergo “bora‐Nazarov”‐type ring‐closing rearrangements upon photolysis. A DFT study had shown that the dienylborane cyclization of such systems itself is endothermic, but a subsequent C6F5 migration is very favorable. Furthermore, substituted 2,5‐dihydroborole products are derived from cyclization and C6F5 migration from the photolysis reaction. In the case of the six‐membered annulation product, a subsequent stereoisomerization reaction takes place and the resultant compound undergoes a P/B FLP 1,2‐addition reaction with a terminal alkyne with rearrangement. 相似文献
38.
Dr. Ramesh C. Samanta Prof. Hisashi Yamamoto 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(34):11976-11979
Electrophilic halogenation is used to produce a wide variety of halogenated compounds. Previously reported methods have been developed mainly using a reagent‐based approach. Unfortunately, a suitable “catalytic” process for halogen transfer reactions has yet to be achieved. In this study, arylamines have been found to generate an N‐halo arylamine intermediate, which acts as a highly reactive but selective catalytic electrophilic halogen source. A wide variety of heteroaromatic and aromatic compounds are halogenated using commercially available N‐halosuccinimides, for example, NCS, NBS, and NIS, with good to excellent yields and with very high selectivity. In the case of unactivated double bonds, allylic chlorides are obtained under chlorination conditions, whereas bromocyclization occurs for polyolefin. The reactivity of the catalyst can be tuned by varying the electronic properties of the arene moiety of catalyst. 相似文献
39.
Dr. Kei Kitamura Dr. Naoyuki Shimada Dr. Craig Stewart Dr. Abdurrahman C. Atesin Prof. Tülay A. Ateşin Prof. Dr. Marcus A. Tius 《Angewandte Chemie (International ed. in English)》2015,54(21):6288-6291
A Pd0‐catalyzed asymmetric Nazarov‐type cyclization is described. The optimized ligand for the reaction incorporates a weakly coordinating pyridine ring into a TADDOL‐derived phosphoramidite (TADDOL=α,α,α,α‐tetraaryl‐1,3‐dioxolane‐4,5‐dimethanol). The reaction leads to the formation of cyclopentenones as single diastereoisomers that incorporate two contiguous asymmetric centers, one tertiary and one an all‐carbon‐atom quaternary stereocenter, in high yield and optical purity. It is noteworthy that the reaction does not require that substrates should be activated by aryl substituents. 相似文献
40.