Control of Diastereoselectivity for Iridium-Catalyzed Allylation of a Prochiral Nucleophile with a Phosphate Counterion

被引:157
作者
Chen, Wenyong [1 ]
Hartwig, John F. [1 ]
机构
[1] Univ Calif Berkeley, Dept Chem, Berkeley, CA 94720 USA
关键词
ALLYLIC SUBSTITUTIONS; AMINO-ACIDS; PHOSPHORAMIDITE LIGANDS; ALKYLATION;
D O I
10.1021/ja311363a
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
We report a highly diastereo- and enantio-selective allylation of azlactones catalyzed by the combination of a metallacyclic iridium complex and an optically inactive phosphate anion. The process demonstrates an approach for conducting diastereoselective reactions with prochiral nucleophiles in the presence of metallacyclic allyliridium complexes. The reaction provides access to an array of enantioenriched allylated azlactones containing adjacent tertiary and quaternary carbon centers. Preliminary mechanistic studies suggest that the phosphate and methyl carbonate anions together induce the unusually high diastereoselectivity.
引用
收藏
页码:2068 / 2071
页数:4
相关论文
共 26 条
[1]   Oxazolones in Organocatalysis, New Tricks for an Old Reagent [J].
Alba, Andrea-Nekane R. ;
Rios, Ramon .
CHEMISTRY-AN ASIAN JOURNAL, 2011, 6 (03) :720-734
[2]   Enantioselective IrI-Catalyzed Carbocyclization of 1,6-Enynes by the Chiral Counterion Strategy [J].
Barbazanges, Marion ;
Auge, Mylene ;
Moussa, Jamal ;
Amouri, Hani ;
Aubert, Corinne ;
Desmarets, Christophe ;
Fensterbank, Louis ;
Gandon, Vincent ;
Malacria, Max ;
Ollivier, Cyril .
CHEMISTRY-A EUROPEAN JOURNAL, 2011, 17 (49) :13789-13794
[3]   Iridium-Catalyzed Regioselective and Enantioselective Allylation of Trimethylsiloxyfuran [J].
Chen, Wenyong ;
Hartwig, John F. .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2012, 134 (37) :15249-15252
[4]   Iridium-catalyzed enantioselective allylic substitutions with aliphatic nitro compounds as prenucleophiles [J].
Dahnz, A ;
Helmchen, G .
SYNLETT, 2006, (05) :697-700
[5]   Enantioselective iridium-catalyzed allylic alkylations -: Improvements and applications based on salt-free reaction conditions [J].
Gnamm, Christian ;
Foerster, Sebastian ;
Miller, Nicole ;
Broedner, Kerstin ;
Helmchen, Guenter .
SYNLETT, 2007, (05) :790-794
[6]   Iridium-Catalyzed Allylic Substitution [J].
Hartwig, John F. ;
Pouy, Mark J. .
IRIDIUM CATALYSIS, 2011, 34 :169-208
[7]   Mechanistically Driven Development of Iridium Catalysts for Asymmetric Allylic Substitution [J].
Hartwig, John F. ;
Stanley, Levi M. .
ACCOUNTS OF CHEMICAL RESEARCH, 2010, 43 (12) :1461-1475
[8]  
Helmchen G., 2009, Iridium Complexes in Organic Synthesis, P211
[9]   Synthesis of β-substituted α-amino acids with use of iridium-catalyzed asymmetric allylic substitution [J].
Kanayama, T ;
Yoshida, K ;
Miyabe, H ;
Kimachi, T ;
Takemoto, Y .
JOURNAL OF ORGANIC CHEMISTRY, 2003, 68 (16) :6197-6201
[10]   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