Reference

Alkylation of a chiral hydrazone by means of asymmetric addition of Grignard reagents to the carbon-nitrogen double bond

Alkylation of a chiral hydrazone by means of asymmetric addition of Grignard reagents to the carbon-nitrogen double bond. Takahashi, Hiroshi; Suzuki, Yuji (Inst. Med. Chem., Hoshi Univ., Tokyo 142, Japan). Chem. Pharm. Bull., 31(12), 4295-9 (English) 1983. CODEN: CPBTAL. ISSN: 0009-2363. 2026-48-4 and 89876-66-4 are cas registry numbers of chemicals which are used as reagents here. DOCUMENT TYPE: Journal CA Section: 22 (Physical Organic Chemistry) (E)-(S)-PhCH:NNMeCH(CHMe2)CH2OH (I) was synthesized from (S)-valinol. I was treated with Grignard reagents to give optically pure PhCHRNHNMeCH(CHMe2)CH2OH (II; R = Me, Et). However, II (R = PhCH2, 4-MeOC6H4CH2) were each obtained as a mixt. of two diastereomers. Nitrogen-nitrogen bonds of II (R = Me, Et) were cleaved by hydrogenolysis to give (S)-PhCHRNH2, and their abs. configurations and optical purities were confirmed. These reactions were assumed to proceed via the chelated six-membered ring intermediates. .

Synthesis of C2-symmetric and unsymmetrically substituted 2,2'-dipyridylamines and crystal structure of a chiral 2,2'-dipyridylamine copper(II) complex

Synthesis of C2-symmetric and unsymmetrically substituted 2,2'-dipyridylamines and crystal structure of a chiral 2,2'-dipyridylamine copper(II) complex. Bolm, Carsten; Frison, Jean-Cedric; Le Paih, Jacques; Moessner, Christian; Raabe, Gerhard (Institut fuer Organische Chemie der RWTH Aachen, Aachen D-52056, Germany). 819084-02-1 and 2026-48-4 are also occured in this study. Journal of Organometallic Chemistry, 689(23), 3767-3777 (English) 2004 Elsevier B.V. CODEN: JORCAI. ISSN: 0022-328X. DOCUMENT TYPE: Journal CA Section: 25 (Benzene, Its Derivatives, and Condensed Benzenoid Compounds) Section cross-reference(s): 27, 29, 75 C2-sym. and unsym. substituted 2,2'-dipyridylamines have been synthesized by sequential Buchwald-Hartwig amination of halo-pyridines. The X-ray crystal structure of a copper dichloride complex bearing a C2-sym. 2,2'-dipyridylamine reveals details of the binding properties of the ligand and the coordination geometry at the metal center. In preliminary expts. the use of the new nitrogen chelates in asym. catalysis has been demonstrated. An example ligand thus prepd. was (-)-(6R,8R)-N-(2-pyridinyl)-5,6,7,8-tetrahydro-7,7-dimethyl-6,8-methano quinolin-2-amine (I). .