Balletti Matteo, Wachsmuth Tommy, Di Sabato Antonio, Hartley Will C, Melchiorre Paolo
ICIQ - Institute of Chemical Research of Catalonia 43007 Tarragona Spain.
Department of Industrial Chemistry 'Toso Montanari', University of Bologna 40136 Bologna Italy
Chem Sci. 2023 Apr 14;14(18):4923-4927. doi: 10.1039/d3sc01347b. eCollection 2023 May 10.
Herein, we report a photochemical organocatalytic method for the asymmetric introduction of perfluoroalkyl fragments (including the valuable trifluoromethyl moiety) at the remote γ-position of α-branched enals. The chemistry exploits the ability of extended enamines (dienamines) to form photoactive electron donor-acceptor (EDA) complexes with perfluoroalkyl iodides, which under blue light irradiation generate radicals through an electron transfer mechanism. The use of a chiral organocatalyst, derived from -4-hydroxy-l-proline, secures a consistently high stereocontrol while inferring complete site selectivity for the more distal γ position of the dienamines.
在此，我们报道了一种光化学有机催化方法，用于在α-支链烯醛的远程γ位不对称引入全氟烷基片段（包括有价值的三氟甲基部分）。该化学方法利用了烯胺（双烯胺）与全氟烷基碘形成光活性电子供体-受体（EDA）配合物的能力，在蓝光照射下，通过电子转移机制产生自由基。使用源自-4-羟基-L-脯氨酸的手性有机催化剂，在确保对双烯胺更远端的γ位具有完全位点选择性的同时，能持续实现高度的立体控制。
