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Gram‐Scale Enantioselective Formal Synthesis of Morphine through an ortho–para Oxidative Phenolic Coupling Strategy 下载免费PDF全文
Dr. Matthieu Tissot Dr. Robert J. Phipps Dr. Catherine Lucas Dr. Rafael M. Leon Dr. Robert D. M. Pace Dr. Tifelle Ngouansavanh Prof. Matthew J. Gaunt 《Angewandte Chemie (International ed. in English)》2014,53(49):13498-13501
A gram‐scale catalytic enantioselective formal synthesis of morphine is described. The key steps of the synthesis involve an ortho–para oxidative phenolic coupling and a highly diastereoselective “desymmetrization” of the resulting cyclohexadienone that generates three of the four morphinan ring junction stereocenters in one step. The stereochemistry is controlled from a single carbinol center installed through catalytic enantioselective hydrogenation. These transformations enabled the preparation of large quantities of key intermediates and could support a practical and scalable synthesis of morphine and related derivatives. 相似文献
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Prof. Dr. Pauline Chiu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(41):14287-14291
An efficient formal total synthesis of (+) cortistatins A and J has been accomplished, by exploiting a highly diastereoselective intramolecular [4+3] cycloaddition of epoxy enolsilanes as the key reaction to construct rings B and C of the cortistatins in one step. 相似文献
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Dr. James D. Firth Dr. Steven J. Canipa Dr. Leigh Ferris Prof. Peter O'Brien 《Angewandte Chemie (International ed. in English)》2018,57(1):223-226
An 8‐step, gram‐scale synthesis of the (?)‐sparteine surrogate (22 % yield, with just 3 chromatographic purifications) and a 10‐step, gram‐scale synthesis of (?)‐sparteine (31 % yield) are reported. Both syntheses proceed with complete diastereocontrol and allow access to either antipode. Since the syntheses do not rely on natural product extraction, our work addresses long‐term supply issues relating to these widely used chiral ligands. 相似文献
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Stereoselective Total Synthesis of Hetisine‐type C20‐Diterpenoid Alkaloids: Spirasine IV and XI 下载免费PDF全文
Quanzheng Zhang Zhongshan Zhang Zhong Huang Changhui Zhang Song Xi Prof. Dr. Min Zhang 《Angewandte Chemie (International ed. in English)》2018,57(4):937-941
The first total synthesis of the architecturally complex hetisine‐type heptacyclic C20‐diterpenoid alkaloids (±)‐spirasine IV and XI is reported. The A/F/G/C tetracyclic skeleton with the challenging N?C6 and C14?C20 linkages was efficiently constructed by an intramolecular azomethine‐ylide‐based 1,3‐dipolar cycloaddition with unusual regioselectivity. SmI2‐mediated free‐radical addition to the arene moiety without prior dearomatization and a stereoselective intramolecular aldol reaction further enabled rapid access to the hetisine core, providing a bicyclo[2.2.2]octane ring with a new oxygen substitution pattern. 相似文献
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Hong-Xiu Huang Fen Mi Chunxin Li Huan He Prof. Dr. Feng-Peng Wang Prof. Dr. Xiao-Yu Liu Prof. Dr. Yong Qin 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(52):23815-23820
The first total synthesis of liangshanone, a hexacyclic ent-kaurane diterpenoid alkaloid, has been completed. Its intricate cagelike framework was assembled through several key transformations, including an oxidative dearomatization/Diels–Alder (OD/DA) cycloaddition sequence, a tandem alkene cleavage/Mannich cyclization, a Robinson-type annulation, and an intramolecular aldol reaction. Notably, an organocatalytic enantioselective α-hydroxymethylation process allowed the preparation of an enantiomerically enriched tricyclic intermediate that should enable asymmetric access to the target natural product. 相似文献
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Jia‐Qiang Dong Henry N. C. Wong Prof. Dr. 《Angewandte Chemie (International ed. in English)》2009,48(13):2351-2354
Piecing it together : The first total synthesis of naturally occurring diterpene pallavicinolide A was achieved. Notable features are highlighted by three key biomimetic transformations: a base‐promoted Grob fragmentation, a singlet oxygen oxidation, and an intramolecular Diels–Alder cycloaddition.
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Short Chemoenzymatic Total Synthesis of ent‐Hydromorphone: An Oxidative Dearomatization/Intramolecular [4+2] Cycloaddition/Amination Sequence 下载免费PDF全文
Vimal Varghese Prof. Tomas Hudlicky 《Angewandte Chemie (International ed. in English)》2014,53(17):4355-4358
A short synthesis of ent‐hydromorphone has been achieved in twelve steps from β‐bromoethylbenzene. The key transformations involved the enzymatic dihydroxylation of the arene to the corresponding cis‐dihydrodiol, Mitsunobu coupling with the ring A fragment, oxidative dearomatization of the C3 phenol, and the subsequent [4+2] cycloaddition to form ring B of the morphinan. The synthesis was completed by intramolecular amination at C9. 相似文献
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Ryosuke Yamada Dr. Yohei Adachi Dr. Satoshi Yokoshima Prof. Tohru Fukuyama 《Angewandte Chemie (International ed. in English)》2016,55(20):6067-6070
Total synthesis of (?)‐daphenylline, a hexacyclic Daphniphyllum alkaloid, was achieved. Construction of the tricyclic DEF ring system was initiated by asymmetric Negishi coupling followed by an intramolecular Friedel–Crafts reaction. Installation of a side chain onto the tricyclic core was carried out through Sonogashira coupling, stereocontrolled Claisen rearrangement by taking advantage of the characteristic conformation of the tricyclic DEF core, and the stereoselective alkylation of a lactone. After the introduction of a glycine unit, the ABC ring system was stereoselectively constructed through intramolecular cycloaddition of the cyclic azomethine ylide. 相似文献
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Dr. Zhiqiang Ma Dr. Ruining Li Zhen Zhang Cheng Tao Dr. Bin Cheng Dr. Yun Li Dr. Huifei Wang Prof. Dr. Hongbin Zhai 《Angewandte Chemie (International ed. in English)》2016,55(38):11638-11641
Described herein is the first asymmetric total synthesis of (+)‐harringtonolide, a natural diterpenoid with an unusual tropone imbedded in a cagelike framework. The key transformations include an intramolecular Diels–Alder reaction and a rhodium‐complex‐catalyzed intramolecular [3+2] cycloaddition to install the tetracyclic core as well as a highly efficient tropone formation. 相似文献
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Qilin Li Prof. Dr. Hongbin Zhang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(46):16379-16382
In this paper, a new strategy towards the synthesis of codeine and morphine is reported. This new approach features a cascade cyclization to construct the dihydrofuran ring, and an intramolecular palladium catalyzed C?H olefination of unactivated aliphatic alkene to install the morphinan ring system. 相似文献
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Roberto Ballette Dr. Maria Pérez Dr. Stefano Proto Prof. Dr. Mercedes Amat Prof. Dr. Joan Bosch 《Angewandte Chemie (International ed. in English)》2014,53(24):6202-6205
Madangamines are a group of bioactive marine sponge alkaloids, embodying an unprecedented diazapentacyclic skeletal type. The enantioselective total synthesis of madangamine D has been accomplished, and represents the first total synthesis of an alkaloid of the madangamine group. It involves the stereoselective construction of the diazatricyclic ABC core using a phenylglycinol‐derived lactam as the starting enantiomeric scaffold and the subsequent assembly of the peripheral macrocyclic rings. The synthesis provides, for the first time, a pure sample of madangamine D and confirms the absolute configuration of this alkaloid family. 相似文献
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Palladium‐Catalyzed Decarbonylative Dehydration for the Synthesis of α‐Vinyl Carbonyl Compounds and Total Synthesis of (−)‐Aspewentins A,B, and C 下载免费PDF全文
Yiyang Liu Dr. Scott C. Virgil Prof. Robert H. Grubbs Prof. Brian M. Stoltz 《Angewandte Chemie (International ed. in English)》2015,54(40):11800-11803
The direct α‐vinylation of carbonyl compounds to form a quaternary stereocenter is a challenging transformation. It was discovered that δ‐oxocarboxylic acids can serve as masked vinyl compounds and be unveiled by palladium‐catalyzed decarbonylative dehydration. The carboxylic acids are readily available through enantioselective acrylate addition or asymmetric allylic alkylation. A variety of α‐vinyl quaternary carbonyl compounds are obtained in good yields, and an application in the first enantioselective total synthesis of (?)‐aspewentins A, B, and C is demonstrated. 相似文献