The Use of Sodium Metal in the Birch Reduction of Aromatic Compounds¹

C‐Linked Disaccharide Analogue of the Thomsen–Friedenreich (T)‐Epitope α‐O‐Conjugated to L‐Serine

“…Inspired by the work of Wong and co-workers, [15] we converted the N-benzyl-N-methoxyamino group of 7 into the corresponding primary amine 11 under Birchs conditions [16] with subsequent catalytic (Pd/C, H 2 ) hydrogenation (Scheme 5).…”

Palladium‐Catalyzed Insertion of an Allene into an Aminal: Aminomethylamination of Allenes by CN Bond Activation

“…The double bond of 3 aa could be selectively reduced by Na/NH 3 to give product 5. [10] Furthermore, the two benzyl groups of 3 la were rapidly removed to give 6 by treatment with CAN in MeOH/H 2 O at room temperature; 6 could then be successfully transformed into tetrahydroquinoline 7, which contains an aminomethyl group, through sequential CÀN coupling and hydrogenation. Furthermore, 1,2-dihydroquinoline 8, which resulted from the C À N coupling reaction, could be isolated and selectively oxidized by [{RuCl 2 (benzene)} 2 ]/TBHP to give the corresponding 2-quinolinone derivative 9 in good yield.…”

“…The p-allylpalladium complex was fully characterized by 1 H, 13 C, and 31 P NMR spectroscopy as well as highresolution mass spectrometry (see the Supporting Information). Furthermore, an X-ray crystal structure of II was obtained, [9] which revealed that an unsymmetric allyl ligand with an aminomethyl moiety (CH 2 NBn 2 )is coordinated to the Pd center in an h 3 mode, and that the Ph group is oriented anti to the attached CH 2 NBn 2 group. This solid-state structure correlated well with the 1 H and 31 P NMR data; in the 31 P NMR spectrum, two doublets could be seen, which is consistent with the unsymmetric nature of the structure shown in Scheme 2.…”

“…The structure of 3 aa was confirmed by single-crystal X-ray analysis (see the Supporting Information). [9] In addition, the undesired allylic amine 4 aa was isolated in 22 % yield, which might result from the off-cycle Scheme 1. Palladium-catalyzed difunctionalization of allenes.…”

Ytterbium(0)

“…Application of this reduction to a derivative of estrone resulted, after hydrolysis of the intermediate enol ether, in dihydrotestosterone (eq 4) 15. In this case, no proton donor was added to the medium.…”