Chemistry - A European Journal p. 12190 - 12200 (2014)
Update date:2022-08-05
Topics:
Zenzola, Marina
Degennaro, Leonardo
Trinchera, Piera
Carroccia, Laura
Giovine, Arianna
Romanazzi, Giuseppe
Mastrorilli, Piero
Rizzi, Rosanna
Pisano, Luisa
Luisi, Renzo
This work demonstrates how the directing ability of the azetidine ring could be useful for regioselective ortho-C-H functionalization of aryl compounds. Robust polar organometallic (lithiated) intermediates are involved in this synthetic strategy. The reagent n-hexyllithium emerged as a safer, yet still effective, basic reagent for the hydrogen/lithium permutation relative to the widely used reagent nBuLi. Two different reaction protocols were discovered for regioselective lithiation at the ortho positions adjacent to the azetidine ring, which served as a toolbox when other competing directing groups were installed on the aromatic ring. The coordinating ability of the azetidine nitrogen atom, as well as the involvement of dynamic phenomena related to the preferential conformations of 2-arylazetidine derivatives, were recognized to be responsible for the observed reactivity and regioselectivity. A site-selective functionalization of the aromatic ring was achieved for aryl azetidines with either coordinatively competent groups (e.g. methoxy) or inductively electron-withdrawing substituents (e.g. chlorine and fluorine). By fine-tuning the reaction conditions, regioselective introduction of several substituents on the aromatic ring could be realized. Several substitution patterns were accomplished, which included 1,2,3-trisubstitution, 1,2,3,4-tetrasubstitution, and 1,2,3,4,5-pentasubstitution, up to the exhaustive substitution of the aromatic ring.
View MoreZhangjiagang Jianing Import & Export Co.,Ltd.
Contact:086-512-55379012 13913607595
Address:NO.1 Guotai North Road Zhangjiagang Economic Development Zone,215600,Jiangsu,China
Shandong Bolode Bio-Technology Co., LTD
Contact:+86-0531-58966870
Address:136 Jingyi Road,Huaiyin District,Jinan,Shandong,China
wuxi huabin bio-tech Co.,Ltd(expird)
Contact:86-0510-85133006
Address:hubin road NO157
Contact:86-28-61993785
Address:No.70-13-21, North Section, Erhuan
SHANXI JINJIN CHEMICAL INDUSTRIAL CO.,LTD
website:http://www.jinjingroup.com
Contact:4009982989
Address:Economic And Technological Development Zone,Hejin?City,Shanxi Province?,China
Doi:10.1016/S0040-4039(98)02616-1
(1999)Doi:10.1002/cjoc.201400167
(2015)Doi:10.1002/chem.201304331
(2014)Doi:10.1016/S0040-4039(00)99607-2
(1989)Doi:10.1016/j.bioorg.2014.02.002
(2014)Doi:10.1002/ejoc.201301806
(2014)