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Palladium

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¡¾ÂÛÎÄÌâÄ¿¡¿£ºOxidative Addition of Ammonia to Form a Stable Monomeric Amido Hydride Complex
¡¾×÷Õß¡¿£ºZhao, J., Goldman, A. S., and J. F. Hartwig
¡¾µ¥Î»¡¿£ºYale University
¡¾ÆÚ¿¯Ãû³Æ¡¿£ºScience
¡¾Ä꣬¾í£¬Ò³¡¿£º2005. 307(5712): p. 1080-1082.
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ÕâÊÇYaleµÄÅ£ÈËJohn F. Hartwig½ÌÊÚµÄ×÷Æ·£¬ËûÊǽðÊô´ß»¯·½ÃæµÄר¼Ò¡£

Zhao, J., Goldman, A. S., and J. F. Hartwig, Oxidative Addition of Ammonia to Form a Stable Monomeric Amido Hydride Complex. Science, 2005. 307(5712): p. 1080-1082.



ÄÚÈݼò½é£ºThe insertion of an iridium complex into an N-H bond in ammonia leads to a stable monomeric amido hydride complex in solution at room temperature. This reaction advances the transition-metal coordination chemistry of ammonia beyond its role for more than a century as an ancillary ligand. The precursor for this insertion reaction is an iridium(I) olefin complex with an aliphatic ligand containing one carbon and two phosphorus donor atoms. Kinetic and isotopic labeling studies indicate that olefin dissociates to give a 14-electron iridium(I) fragment, which then reacts with ammonia. This
cleavage of the N-H bond under neutral conditions provides a foundation on which to develop future mild catalytic transformations of ammonia, such as olefin hydroamination and arene oxidative amination.

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¡¾ÂÛÎÄÌâÄ¿¡¿£ºIonic Liquid-Promoted, Highly Regioselective Heck Arylation of Electron-Rich Olefins by Aryl Halides
¡¾×÷Õß¡¿£ºMo, J.; Xu, L.; Xiao, J.
¡¾µ¥Î»¡¿£ºUniversity of Liverpool
¡¾ÆÚ¿¯Ãû³Æ¡¿£ºJ. Am. Chem. Soc.
¡¾Ä꣬¾í£¬Ò³¡¿£º2005; 127(2); 751-760.
¡¾Ó°ÏìÒò×Ó¡¿£º6.9

Ionic Liquid-Promoted, Highly Regioselective Heck Arylation of Electron-Rich Olefins by Aryl Halides
Mo, J.; Xu, L.; Xiao, J.
J. Am. Chem. Soc.; (Article); 2005; 127(2); 751-760.  DOI: 10.1021/ja0450861

http://pubs3.acs.org/acs/journal ... i=10.1021/ja0450861



Abstract:

Palladium-catalyzed regioselective Heck arylation of the electron-rich olefins, vinyl ethers 1a-d, enamides 1e-g, and allyltrimethylsilane 1h, has been accomplished in imidazolium ionic liquids with a wide range of aryl bromides and iodides instead of the commonly used, but commercially unavailable and expensive, aryl triflates. The reaction proceeded with high efficiency and remarkable regioselectivity without the need for costly or toxic halide scavengers, leading exclusively to substitution by aryl groups of diverse electronic and steric properties at the olefinic carbon  to the heteroatom of 1a-g and  to the heteroatom of 1h. In contrast, the arylation reaction in molecular solvents led to mixtures of regioisomers under similar conditions. Several lines of evidence point to the unique regiocontrol stemming from the ionic environment provided by the ionic liquid that alters the reaction pathway. The chemistry provides a simple, effective method for preparing branched, arylated olefins and contributes to the extension of Heck reaction to a wider range of substrates.

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Palladium

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¡¾ÂÛÎÄÌâÄ¿¡¿£ºVersatile Catalysts for the Suzuki Cross-Coupling of Arylboronic Acids with Aryl and Vinyl Halides and Triflates under Mild Conditions
¡¾×÷Õß¡¿£ºLittke, A. F.; Dai, C.; Fu, G. C.
¡¾µ¥Î»¡¿£ºMIT
¡¾ÆÚ¿¯Ãû³Æ¡¿£ºJ. Am. Chem. Soc.
¡¾Ä꣬¾í£¬Ò³¡¿£º2000; 122(17); 4020-4028.
¡¾Ó°ÏìÒò×Ó¡¿£º6.9


Fu, G. C. ÊÇMITµÄ×ÊÉî½ÌÊÚ£¬Ò²ÊÇJACSµÄ±à¼­Ö®Ò»¡£ÕæÕýµÄ´óÅ£¡£


Versatile Catalysts for the Suzuki Cross-Coupling of Arylboronic Acids with Aryl and Vinyl Halides and Triflates under Mild Conditions
Littke, A. F.; Dai, C.; Fu, G. C.
J. Am. Chem. Soc.; (Article); 2000; 122(17); 4020-4028.  DOI: 10.1021/ja0002058

http://pubs3.acs.org/acs/journal ... i=10.1021/ja0002058


Abstract:

Through the use of Pd2(dba)3/P(t-Bu)3 as a catalyst, a wide range of aryl and vinyl halides, including chlorides, undergo Suzuki cross-coupling with arylboronic acids in very good yield, typically at room temperature; through use of Pd(OAc)2/PCy3, a diverse array of aryl and vinyl triflates react cleanly at room temperature. Together, these two catalyst systems cover a broad spectrum of commonly encountered substrates for Suzuki couplings. Furthermore, they display novel reactivity patterns, such as the selective cross-coupling by Pd2(dba)3/P(t-Bu)3 of an aryl chloride in preference to an aryl triflate, and they can be used at low loading, even for reactions of aryl chlorides. Preliminary mechanistic work indicates that a palladium monophosphine complex is the active catalyst in the cross-coupling of aryl halides.

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[ Last edited by Palladium on 2006-5-26 at 19:29 ]
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paracyclophane

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¡¾ÂÛÎÄÌâÄ¿¡¿£ºCatalysts for Suzuki-Miyaura Coupling Processes: Scope and Studies of the Effect of Ligand Structure
¡¾×÷Õß¡¿£ºStephen L. Buchwald
¡¾µ¥Î»¡¿£ºContribution from the Department of Chemistry, Massachusetts Institute of Technology,Cambridge, Massachusetts 02139
¡¾ÆÚ¿¯Ãû³Æ¡¿£ºJ. AM. CHEM. SOC.
¡¾Ä꣬¾í£¬Ò³¡¿£º2005, 127, 4685-4696
¡¾Ó°ÏìÒò×Ó¡¿£º6.9



    À´×ÔMITµÄÅ£ÈËStephen L. Buchwald¡£

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tanduanming

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