Chasing the proton culprit from palladium-catalyzed allylic amination

被引:81
作者
Dubovyk, Igor [1 ]
Watson, Iain D. G. [1 ]
Yudin, Andrei K. [1 ]
机构
[1] Univ Toronto, Dept Chem, Davenport Res Labs, Toronto, ON M5S 3H6, Canada
关键词
D O I
10.1021/ja076659n
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
We have found that the addition of base has a significant effect on palladium-catalyzed allylic amination. The long-standing problem of controlling the branched-to-linear ratio has been solved. In the presence of DBU and inexpensive, readily available ligands, palladium-catalyzed allylation proceeds under kinetic control, leading to high branched selectivity. Given the widespread utility of palladium-catalyzed allylic amination, we expect that these findings will be relevant in many areas ranging from asymmetric catalysis to target-oriented synthesis.
引用
收藏
页码:14172 / +
页数:3
相关论文
共 28 条
[1]   AMINATION OF PI-ALLYLPALLADIUM CHLORIDE COMPLEXES - A MECHANISTIC STUDY [J].
AKERMARK, B ;
AKERMARK, G ;
HEGEDUS, LS ;
ZETTERBERG, K .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1981, 103 (11) :3037-3040
[2]   Palladium(0)-catalyzed allylic aminations:: Kinetics and mechanism of the reaction of secondary amines with cationic [(η3-allyl)PdL2]+ complexes [J].
Amatore, Christian ;
Genin, Emilie ;
Jutand, Anny ;
Mensah, Laure .
ORGANOMETALLICS, 2007, 26 (08) :1875-1880
[3]   Proton-catalyzed hydroamination and hydroarylation reactions of anilines and alkenes: A dramatic effect of counteranions on reaction efficiency [J].
Anderson, LL ;
Arnold, J ;
Bergman, RG .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2005, 127 (42) :14542-14543
[4]   Simultaneous generation of anionic and neutral palladium(II) complexes from η3-allylpalladium chloride dimer and fluorinated β-enaminones [J].
Bouquillon, S ;
Bouillon, JP ;
Thomas, L ;
Plantier-Royon, R ;
Chanteau, F ;
Tinant, B ;
Hénin, F ;
Portella, C ;
Muzart, J .
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, 2003, 2003 (24) :4717-4720
[5]   Enantiospecific synthesis of allylamines via the regioselective rhodium-catalyzed allylic amination reaction (vol 121, pg 6761, 1999) [J].
Evans, PA ;
Robinson, JE ;
Nelson, JD .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1999, 121 (51) :12214-12214
[6]   Palladium/BINAP(S)-catalyzed asymmetric allylic amination [J].
Faller, JW ;
Wilt, JC .
ORGANIC LETTERS, 2005, 7 (04) :633-636
[7]   ASYMMETRIC ALLYLIC AMINATION CATALYZED BY CHIRAL FERROCENYLPHOSPHINE-PALLADIUM COMPLEXES [J].
HAYASHI, T ;
KISHI, K ;
YAMAMOTO, A ;
ITO, Y .
TETRAHEDRON LETTERS, 1990, 31 (12) :1743-1746
[8]   Primary tert- and sec-allylamines via palladium-catalyzed hydroamination and allylic substitution with hydrazine and hydroxylamine derivatives [J].
Johns, Adam M. ;
Liu, Zhijian ;
Hartwig, John F. .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2007, 46 (38) :7259-7261
[9]   Enantio- and diastereoselective Ir-catalyzed allylic substitutions for asymmetric synthesis of amino acid derivatives [J].
Kanayama, T ;
Yoshida, K ;
Miyabe, H ;
Takemoto, Y .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2003, 42 (18) :2054-2056
[10]   Identification of an activated catalyst in the iridium-catalyzed allylic amination and etherification. Increased rates, scope, and selectivity [J].
Kiener, CA ;
Shu, CT ;
Incarvito, C ;
Hartwig, JF .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2003, 125 (47) :14272-14273