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Journal ArticleDOI

Copper-catalyzed coupling of amides and carbamates with vinyl halides.

09 Sep 2003-Organic Letters (Org Lett)-Vol. 5, Iss: 20, pp 3667-3669
TL;DR: A general and efficient copper-catalyzed method for the amidation of vinyl bromides and iodides has been developed and the double bond geometry of the vinyl halides was retained under the reaction conditions.
About: This article is published in Organic Letters.The article was published on 2003-09-09. It has received 360 citations till now. The article focuses on the topics: Silyl ether & Double bond.
Citations
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Journal ArticleDOI
TL;DR: Using R-Hydroxy Stannanes as a Model for a Methylenation Reaction and Conclusions and Future Prospects are presented.
Abstract: 6.4. Polyynes 3123 6.5. Using R-Hydroxy Stannanes 3124 6.6. Using the Hurtley Reaction 3124 6.7. Using a Methylenation Reaction 3125 7. Conclusions and Future Prospects 3125 8. Uncommon Abbreviations 3125 9. Acknowledgments 3125 10. Note Added in Proof 3125 11. References 3126 * Authorstowhomcorrespondenceshouldbeaddressed(evano@chimie.uvsq.fr, nicolas.blanchard@uha.fr). † Université de Versailles Saint Quentin en Yvelines. ‡ Université de Haute-Alsace. Chem. Rev. 2008, 108, 3054–3131 3054

1,789 citations

Journal ArticleDOI
TL;DR: A number of methods using various copper complexes and salts to carry out cross-coupling reactions leading to the formation of C heteroatom (C N, C O, C S, C P, C Se), C C, and C metal bonds have been proposed as discussed by the authors.

1,361 citations

Journal ArticleDOI
TL;DR: It is demonstrated that an l-proline or N,N-dimethylglycine ligand can facilitate most typical Ullmann-type reactions, with reactions occurring under relatively mild conditions and using only 2-20 mol % copper catalysts.
Abstract: Copper-assisted Ullmann-type coupling reactions are valuable transformations for organic synthesis. Researchers have extensively applied these reactions in both academic and industrial settings. However, two important issues, the high reaction temperatures (normally above 150 °C) and the stoichiometric amounts of copper necessary, have greatly limited the reaction scope. To solve these problems, we and other groups have recently explored the use of special ligands to promote these coupling reactions. We first showed that the structure of α-amino acids can accelerate Cu-assisted Ullmann reactions, leading to the coupling reactions of aryl halides and α-amino acids at 80−90 °C. In response to these encouraging results, we also discovered that an l-proline ligand facilitated the following transformations: (1) coupling of aryl halides with primary amines, cyclic secondary amines, and N-containing heterocycles at 40−90 °C; (2) coupling of aryl halides with sulfinic acid salts at 80−95 °C; (3) azidation of aryl...

932 citations

Journal ArticleDOI
TL;DR: In this tutorial review, highlights of the recent literature have been presented covering the key areas where metal catalysts have been used in amide bond formation.
Abstract: Amongst the many ways of constructing the amide bond, there has been a growing interest in the use of metal-catalysed methods for preparing this important functional group. In this tutorial review, highlights of the recent literature have been presented covering the key areas where metal catalysts have been used in amide bond formation. Acids and esters have been used in coupling reactions with amines, but aldehydes and alcohols have also been used in oxidative couplings. The use of nitriles and oximes as starting materials for amide formation are also emerging areas of interest. The use of carbon monoxide in the transition metal catalysed coupling of amines has led to a powerful methodology for amide bond formation and this is complemented by the addition of an aryl or alkenyl group to an amide typically using palladium or copper catalysts.

826 citations

Journal ArticleDOI
TL;DR: The use of diamine-based ligands has been important in these advances and in this review we discuss these systems, including the choice of reaction conditions and applications in the synthesis of pharmaceuticals, natural products and designed materials as mentioned in this paper.
Abstract: The utility of copper-mediated cross-coupling reactions has been significantly increased by the development of mild reaction conditions and the ability to employ catalytic amounts of copper. The use of diamine-based ligands has been important in these advances and in this review we discuss these systems, including the choice of reaction conditions and applications in the synthesis of pharmaceuticals, natural products and designed materials.

531 citations

References
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Book ChapterDOI
TL;DR: The development of new palladium catalysts for the arylation of amines and alcohols with aryl halides and sulfonates is reviewed in this article, where modifications and improvements in technical aspects of reaction development are described where appropriate.
Abstract: The development of new palladium catalysts for the arylation of amines and alcohols with aryl halides and sulfonates is reviewed. Initial systems as well as mechanistic issues are discussed briefly, while subsequent generations of catalysts are described in greater detail. For these later generations of catalysts, substrate scope and limitations are also discussed. The review is organized by substrate class. Modifications and improvements in technical aspects of reaction development are described where appropriate. In addition, applications of this technology toward natural product synthesis, new synthetic methodology, and medicinal chemistry are chronicled. This review is organized in a manner that is designed to be useful to the synthetic organic chemist.

994 citations

Journal ArticleDOI
TL;DR: Compar pattern-recognition analyses of the NCI 60-cell mean graph screening profiles of 1 did not reveal any significant correlations to the profiles of known antitumor compounds in theNCI's "standard agent database", thus supporting the conclusion that the salicylihalamides represent a potentially important new class for antitumors lead optimization and in vivo investigations.
Abstract: Two novel, highly potent, cytotoxic macrolides, salicylihalamides A (1) and B (2), were isolated from the sponge Haliclona sp. This new macrolide class incorporates salicylic acid, a 12-membered lactone ring, and an enamide side chain. COMPARE pattern-recognition analyses of the NCI 60-cell mean graph screening profiles of 1 did not reveal any significant correlations to the profiles of known antitumor compounds in the NCI's “standard agent database”, thus supporting the conclusion that the salicylihalamides represent a potentially important new class for antitumor lead optimization and in vivo investigations.

247 citations

Journal ArticleDOI
TL;DR: Modified reaction conditions have been developed to synthesize the O-methyloxime enamide side chains related to the natural products lobatamides A-F, oximidine I and II, and CJ-12,950.

195 citations

Journal ArticleDOI
TL;DR: A novel macrolide, apicularen A, was produced by several species of the genus Chondromyces, and is chemically closely related to the salicylihalamides A and B from the marine sponge Haliclona sp.
Abstract: A novel macrolide, apicularen A, was produced by several species of the genus Chondromyces. Initially it was discovered by bioassay-guided RP-HPLC-fractionation of culture extracts of Chondromyces robustus, strain Cm a13. Apicularen A showed no antimicrobial activity, but was highly cytotoxic for cultivated human and animal cells, with IC50 values ranging between 0.1 and 3 ng/ml. A cometabolite of apicularen A, the N-acetylglucosamine glycoside apicularen B, was distinctly less cytotoxic with IC50 values between 0.2 and 1.2 μg/ml, and showed weak activity against a few Gram-positive bacteria. Apicularen A is chemically closely related to the salicylihalamides A and B from the marine sponge Haliclona sp.

152 citations

Journal ArticleDOI
TL;DR: A concise total synthesis of the potent cytotoxic marine natural products salicylihalamide A and B (la, b) is reported.
Abstract: A concise total synthesis of the potent cytotoxic marine natural products salicylihalamide A and B (la, b) is reported. Key steps of our approach were the asymmetric hydrogenation reactions of β-keto esters 18 and 32 catalyzed by [((S)-BINAP)Ru-Cl 2 ] 2 .NEt 3 and the cyclization of the macrolide core by ring closing olefin metathesis (RCM) using the "second-generation" ruthenium carbene complex 24 as the catalyst which bears an imidazol-2-ylidene ligand. The E/Z ratio obtained in this macrocyclization reaction was determined by the protecting groups at the remote phenolic OH group of the cyclization precursor. The elaboration of the resulting cycloalkene 37 into the final target involved a CrCl 2 -mediated synthesis of vinyliodide 49 which, after deprotection, did undergo a copper-catalyzed cross-coupling process with the (Z,Z)-configurated carboxamide 42 to form the labile enamide moiety of 1. Compound 42 was derived from a palladium-catalyzed Negishi coupling between butynylzinc chloride and 3-iodoacrylate 39 followed by a Lindlar reduction of enyne 40 thus obtained and a final aminolysis of the ester group.

141 citations