A Catalytic Reactor for the Organocatalyzed Enantioselective Continuous Flow Alkylation of Aldehydes

被引:25
作者
Porta, Riccardo [1 ]
Benaglia, Maurizio [1 ]
Puglisi, Alessandra [1 ]
Mandoli, Alessandro [3 ]
Gualandi, Andrea [2 ]
Cozzi, Pier Giorgio [2 ]
机构
[1] Univ Milan, Dipartimento Chim, I-20133 Milan, Italy
[2] ALMA MATER STUDIORUM Univ Bologna, Dipartimento Chim G Ciamician, I-40126 Bologna, Italy
[3] Univ Pisa, Dipartimento Chim & Chim Ind, I-56126 Pisa, Italy
关键词
alkylation; catalytic reactor; continuous flow; organocatalysis; stereoselectivity; PRACTICAL CHIRAL AUXILIARY; SPRING HEMLOCK LOOPER; DIELS-ALDER REACTIONS; ALPHA-ALKYLATION; ASYMMETRIC ALKYLATION; PHEROMONE COMPONENTS; HIGHLY EFFICIENT; SEX-PHEROMONE; 7,11-DIMETHYLHEPTADECANE; 7-METHYLHEPTADECANE;
D O I
10.1002/cssc.201402610
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The use of immobilized metal-free catalysts offers the unique possibility to develop sustainable processes in flow mode. The challenging intermolecular organocatalyzed enantioselective alkylation of aldehydes was performed for the first time under continuous flow conditions. By using a packed-bed reactor filled with readily available supported enantiopure imidazolidinone, different aldehydes were treated with three distinct cationic electrophiles. In the organocatalyzed a-alkylation of aldehydes with 1,3-benzodithiolylium tetrafluoroborate, excellent enantioselectivities, in some cases even better than those obtained in the flask process (up to 95%ee at 25 degrees C), and high productivity (more than 3800 h(-1)) were obtained, which thus shows that a catalytic reactor may continuously produce enantiomerically enriched compounds. Treatment of the alkylated products with Raney-nickel furnished enantiomerically enriched a-methyl derivatives, key intermediates for active pharmaceutical ingredients and natural products.
引用
收藏
页码:3534 / 3540
页数:7
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