111923-34-3Relevant articles and documents
Directed Metalation of Aromatic Aldimines with Lithium 2,2,6,6-Tetramethylpiperidide
Flippin, Lee A.,Muchowski, Joseph M.,Carter, David S.
, p. 2463 - 2467 (1993)
N-Cyclohexyl aromatic aldimines are ortho-lithiated or o-methyl-lithiated with 2 equiv of lithium 2,2,6,6-tetramethylpiperidide (LTMP) in THF solution at -15 deg C.The lithiated intermediates generally reacted with alkyl halides or CO2 to provide ortho-functionalized aldimine products which could be readily converted to the corresponding aldehydes by hydrolysis with aqueous 4 M HCl.Aromatic aldimines derived from (+/-)-trans-2-methylcyclohexylamine or 3-amino-2,4-dimethylpentane are resistant toward C=N addition with 1 equiv of n-BuLi at 0 deg C in THF solution; however, they are also surprisingly resistant toward directed metalation reactions with either LTMP or n-BuLi.Exceptions to the ortho-directing and o-methyl-directing effects of the aldimine group were observed in a reaction of 3-methylthiophene-2-carboxaldehyde cyclohexylimine (7) with LTMP, followed by CH3I, which gave a 9:1 mixture of 3,5-dimethylthiophene-2-carboxaldehyde cyclohexylimine (22) and 5-ethyl-3-methylthiophene-2-carboxaldehyde cyclohexylimine (23), and a reaction of p-tolualdehyde 2,4-dimethylpent-3-ylimine (11) with either n-BuLi or LTMP, followed by CH3I, which gave p-ethylbenzaldehyde 2,4-dimethylpent-3-ylimine (25).
Synthesis of aromatic aldehydes by organocatalytic [4+2] and [3+3] cycloaddition of α,β-unsaturated aldehydes
Hong, Bor-Cherng,Tseng, Hsing-Chang,Chen, Shang-Hung
, p. 2840 - 2850 (2007/10/03)
Organocatalytic inter- and intramolecular [4+2] and [3+3] cycloadditions of α,β-unsaturated aldehydes to give polysubstituted aromatic aldehydes are described. High periselectivity for the cycloadditions, with catalyst effects exerted by l-proline and pyrrolidine-HOAc, as well as cocatalyst, additive effects, has been observed.
Synthetic Studies in Diterpene Series: Part XII - Synthesis of (+/-)-14-Ethyl-13-methylpodocarpa-8,11,13-triene - A Precursor of Veadeirol and Veadeiroic Acid
Nasipuri, Dhanonjoy,Mahapatra, Bimal,Samaddar, Ashis K.,Saha, Arabinda
, p. 1112 - 1117 (2007/10/02)
(+/-)-14-Ethyl-13-methylpodocarpa-8,11,13-triene (7) has been synthesised with a view to converting it into veadeirol (1) and veadeiroic acid (2), the two novel diterpenes having the rare cleistanthol skeleton.The key intermediate in the synthesis is 2-et