Direct Formic Acid Mediated Z-Selective Reductive Coupling of Dienes and Aldehydes

被引:19
作者
Cooze, Christopher [1 ,2 ]
Dada, Raphael [1 ,2 ]
Lundgren, Rylan J. [1 ,2 ]
机构
[1] Univ Alberta, Dept Chem, Edmonton T6G 2G2, AB T6G 2G2, Canada
[2] Univ Alberta, Dept Chem, Edmonton, AB T6G 2G2, Canada
基金
加拿大自然科学与工程研究理事会;
关键词
alkenes; chemoselectivity; homogeneous catalysis; reductive coupling; rhodium; FRIEDEL-CRAFTS ALKYLATION; TRANSFER HYDROGENATION; PRIMARY ALCOHOLS; HOMOALLYLIC ALCOHOLS; ASYMMETRIC-SYNTHESIS; CARBONYL ALLYLATION; RUTHENIUM; 1,3-DIENES; ALKYNES; PROPARGYL;
D O I
10.1002/anie.201905540
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Methods for the addition of unsaturated nucleophiles to carbonyls to generate Z-olefin products remain rare and often require either alkyl borane or zinc reductants, limiting their utility. Demonstrated here is that formic acid mediates the Rh-catalyzed, Z-selective coupling of dienes and aldehydes. The process is distinguished by broad tolerance towards reducible or electrophilic groups. Kinetic analysis suggests that generation of the catalytically active Rh intermediate by ligand dissociation is the rate-determining step. The rapid generation and trapping of Rh-allyl intermediates is key to preventing chain-walking isomerization events that plague related protocols. Insights gained through this study may have wider implications in selective metal-catalyzed hydrofunctionalization reactions.
引用
收藏
页码:12246 / 12251
页数:6
相关论文
共 72 条
[1]  
[Anonymous], 2014, ANGEW CHEM-GER EDIT
[2]  
[Anonymous], 2004, ANGEW CHEM
[3]  
[Anonymous], 2015, ANGEW CHEM, V127, P16044
[4]  
[Anonymous], 2005, HDB FUNCTIONALIZED O
[5]   Diastereodivergent Reductive Cross Coupling of Alkynes through Tandem Catalysis: Z- and E-Selective Hydroarylation of Terminal Alkynes [J].
Armstrong, Megan K. ;
Goodstein, Madison B. ;
Lalic, Gojko .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2018, 140 (32) :10233-10241
[6]  
Bower J. F., 2009, ANGEW CHEM, V121, P36
[7]   Catalytic Carbonyl Addition through Transfer Hydrogenation: A Departure from Preformed Organometallic Reagents [J].
Bower, John F. ;
Kim, In Su ;
Patman, Ryan L. ;
Krische, Michael J. .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2009, 48 (01) :34-46
[8]  
Bures J., 2016, Angew. Chem, V128, P16318, DOI [10.1002/ange.201609757, DOI 10.1002/ANGE.201609757]
[9]   Variable Time Normalization Analysis: General Graphical Elucidation of Reaction Orders from Concentration Profiles [J].
Bures, Jordi .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2016, 55 (52) :16084-16087
[10]   A Simple Graphical Method to Determine the Order in Catalyst [J].
Bures, Jordi .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2016, 55 (06) :2028-2031