Journal of the American Chemical Society p. 12860 - 12871 (2003)
Update date:2022-08-05
Topics:
Belokon, Yuri N.
Bespalova, Natalia B.
Churkina, Tatiana D.
Cisarova, Ivana
Ezernitskaya, Marina G.
Harutyunyan, Syuzanna R.
Hrdina, Radim
Kagan, Henri B.
Kocovsky, Pavel
Kochetkov, Konstantin A.
Larionov, Oleg V.
Lyssenko, Konstantin A.
North, Michael
Polasek, Miroslav
Peregudov, Alexander S.
Prisyazhnyuk, Vladimir V.
Vyskocil, Stepan
Achiral, diamagnetic Ni(II) complexes 1 and 3 have been synthesized from Ni(II) salts and the Schiff bases, generated from glycine and PBP (7) and PBA (11), respectively, in MeONa/MeOH solutions. The requisite carbonyl-derivatizing agents pyridine-2-carboxylic acid(2-benzoyl-phenyl)-amide 7 (PBP) and pyridine-2-carboxylic acid(2-formyl-phenyl)-amide 11 (PBA) were readily prepared from picolinic acid and o-aminobenzophenone or picolinic acid and methyl o-anthranilate, respectively. The structure of 1 was established by X-ray crystallography. Complexes 1 and 3 were found to undergo C-alkylation with alkyl halides under PTC conditions in the presence of β-naphthol or benzyltriethylammonium bromide as catalysts to give mono- and bis-alkylated products, respectively. Decomposition of the complexes with aqueous HCI under mild conditions gave the required amino acids, and PBP and PBA were recovered. Alkylation of 1 with highly reactive alkyl halides, carried out under the PTC conditions in the presence of 10% mol of (S)- or (R)-2-hydroxy-2′ -amino-1,1′-binaphthyl 31a (NOBIN) and/or its N-acyl derivatives and by (S)- or (R)-2-hydroxy-8′-amino-1,1′-binaphthyl 32a (iso-NOBIN) and its N-acyl derivatives, respectively, gave rise to α-amino acids with high enantioselectivities (90-98.5% ee) in good-to-excellent chemical yields at room temperature within several minutes. An unusually large positive nonlinear effect was observed in these reactions. The Michael addition of acrylic derivatives 37 to 1 was conducted under similar conditions with up to 96% ee. The 1H NMR and IR spectra of a mixture of the sodium salt of NOBIN and 1 indicated formation of a complex between the two components. Implications of the association and self-association of NOBIN for the observed sense of asymmetric induction and nonlinear effects are discussed.
View MoreLiaoyang hengye Chemical Co., Ltd.
Contact:86-419-5850866
Address:North Old Xiaoxiao Road,Yantai District, Dengta, Liaoyang, Liaoning, China
Shanghai Yudiao Chemistry Technology Co.,Ltd
Contact:0086-18964703211
Address:Building NO.5, NO.218,Rongtian Road,ganxiang town,Jinshan District,shanghai,201518,china
website:http://www.p-oled.cn/
Contact:+86-29-81101199
Address:No. 1199, Dingkunchi 3rd Road, High Tech Zone, Xi'an, Shaanxi, China,710119
ZUNYI CITY BEI YUAN CHEMICAL CO., LTD
website:http://www.china-beiyuan.com
Contact:+86-851-27751258
Address:Wujiang Building, Xianggang Road, Zunyi City, Guizhou Province, China
Shanghai Yudiao Chemistry Technology Co.,Ltd
Contact:0086-18964703211
Address:Building NO.5, NO.218,Rongtian Road,ganxiang town,Jinshan District,shanghai,201518,china
Doi:10.1021/ja00342a040
(1983)Doi:10.1039/c39820001022
(1982)Doi:10.1021/ja0561690
(2005)Doi:10.1081/SCC-120018767
(2003)Doi:10.1016/S0040-4039(00)88677-3
(1982)Doi:10.1016/S0022-328X(00)87042-4
(1982)