Quantitative Evaluation of the Factors Contributing to the “Copper Effect” in the Stille Reaction
作者： Arturo L. Casado , Pablo Espinet
DOI: 10.1021/OM020896B
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摘要: The relative importance of the factors contributing to accelerating effect CuI on [PdL4]-catalyzed couplings R1I and R2SnBu3 (copper effect) has been quantitatively evaluated in THF for R1 = 3,5-C6Cl2F3; R2 vinyl, C6H4-4-OMe; L AsPh3, PPh3, using spectroscopic kinetic methods. 19F NMR data show that rate enhancement produced by addition is strongly related with “autoretardation” intrinsic [PdL4] catalysts almost independent organotin reagent (vinyl, aryl). due release 2 equiv during oxidation yield trans-[PdR1IL2], which species undergoing transmetalation. does not promote dissociation from but it captures part free neutral ligand therefore mitigates autoretardation presence rate-determining associative In conditions studied (Pd:Cu 1:2; T 322.6 K; as solvent), =...
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sci-hub.se 参考文章(14)
John K. Stille, The Palladium‐Catalyzed Cross‐Coupling Reactions of Organotin Reagents with Organic Electrophiles [New Synthetic Methods (58)] Angewandte Chemie. ,vol. 25, pp. 508- 524 ,(1986) , 10.1002/ANIE.198605081
Vittorio Farina, Bala Krishnan, Large rate accelerations in the stille reaction with tri-2-furylphosphine and triphenylarsine as palladium ligands: mechanistic and synthetic implications Journal of the American Chemical Society. ,vol. 113, pp. 9585- 9595 ,(1991) , 10.1021/JA00025A025
Janis Louie, John F. Hartwig, Transmetalation, Involving Organotin Aryl, Thiolate, and Amide Compounds. An Unusual Type of Dissociative Ligand Substitution Reaction Journal of the American Chemical Society. ,vol. 117, pp. 11598- 11599 ,(1995) , 10.1021/JA00151A033
Gary D. Allred, Lanny S. Liebeskind, Copper-Mediated Cross-Coupling of Organostannanes with Organic Iodides at or below Room Temperature Journal of the American Chemical Society. ,vol. 118, pp. 2748- 2749 ,(1996) , 10.1021/JA9541239
Hans H. Cornehl, Christoph Heinemann, Joaquim Marçalo, António Pires de Matos, Helmut Schwarz, THE BARE URANYL(2+) ION, UO22+ Angewandte Chemie. ,vol. 35, pp. 891- 894 ,(1996) , 10.1002/ANIE.199608911
Arturo L. Casado, Pablo Espinet, Mechanism of the Stille Reaction. 1. The Transmetalation Step. Coupling of R1I and R2SnBu3 Catalyzed by trans-[PdR1IL2] (R1 = C6Cl2F3; R2 = Vinyl, 4-Methoxyphenyl; L = AsPh3) Journal of the American Chemical Society. ,vol. 120, pp. 8978- 8985 ,(1998) , 10.1021/JA9742388
Kenji Uneyama, Makoto Momota, Kazuaki Hayashida, Toshiyuki Itoh, Generation and electrophilic reactions of the 2,2,2-trifluoro-1-(phenylthio)ethyl carbocation Journal of Organic Chemistry. ,vol. 55, pp. 5364- 5368 ,(1990) , 10.1021/JO00306A013
Enrique Gomez-Bengoa, Antonio M. Echavarren, Synthesis of isoascididemin, a regioisomer of the marine alkaloid ascididemin Journal of Organic Chemistry. ,vol. 56, pp. 3497- 3501 ,(1991) , 10.1021/JO00011A011
Vittorio Farina, Suresh Kapadia, Bala Krishnan, Chenjie Wang, Lanny S. Liebeskind, On the Nature of the "Copper Effect" in the Stille Cross-Coupling Journal of Organic Chemistry. ,vol. 59, pp. 5905- 5911 ,(1994) , 10.1021/JO00099A018
Michael Hanack, Guenter Renz, Joachim Straehle, Siegbert Schmid, Synthesis and characterization of substituted (1,2-naphthalocyaninato)iron compounds and bisaxially coordinated isocyanide complexes Journal of Organic Chemistry. ,vol. 56, pp. 3501- 3509 ,(1991) , 10.1021/JO00011A012