94256-57-2Relevant academic research and scientific papers
Transition-Metal Free Chemoselective Hydroxylation and Hydroxylation-Deuteration of Heterobenzylic Methylenes
Fu, Yiwei,Li, Hao,Liu, Yonghai,Mang, Zhiguo,Shi, Lei,Sun, Chengyu,Yu, Yang
supporting information, p. 8127 - 8131 (2020/11/03)
We developed an approach for direct selective hydroxylation of heterobenzylic methylenes to secondary alcohols avoiding overoxidation to ketones by using a KOBu-t/DMSO/air system. Most reactions could reach completion in several minutes to give hydroxylated products in 41-76% yields. Using DMSO-d6, this protocol resulted in difunctionalization of heterobenzylic methylenes to afford α-deuterated secondary alcohols (>93% incorporation). By employing this method, active pharmaceutical ingredients carbinoxamine and doxylamine were synthesized in two steps in moderate yields.
Iron-Catalyzed Aerobic Oxidation of (Alkyl)(aryl)azinylmethanes
Sterckx, Hans,Sambiagio, Carlo,Lemière, Filip,Tehrani, Kourosch Abbaspour,Maes, Bert U. W.
, p. 1564 - 1570 (2017/08/11)
An iron-catalyzed aerobic oxidation of (alkyl)(aryl)azinylmethanes has been developed leading to tertiary alcohols in moderate to good yields. Hock rearrangement was identified as a major side reaction leading to a complex mixture of undesired products. Addition of thiourea sometimes allows inhibiting this side reaction and steers the reaction towards the desired products.
Pyridine-directed organolithium addition to an enol ether
Yang, Jingyue,Dudley, Gregory B.
supporting information; experimental part, p. 3438 - 3442 (2011/02/24)
A previously reported anionic rearrangement of benzyl 2-pyridyl ethers can now be accessed by a distinct and unusual mechanism: addition of alkyllithium reagents to α-(2-pyridyloxy)-styrene triggers an anionic rearrangement to afford tertiary pyridyl carbinols. The process is explained by invoking a contra-electronic, pyridine-directed carbolithiation of the enol ether π-system. Copyright
Carbon-carbon bond cleavage of α-hydroxybenzylheteroarenes catalyzed by cyanide ion: Retro-benzoin condensation affords ketones and heteroarenes and benzyl migration affords benzylheteroarenes and arenecarbaldehydes
Suzuki, Yumiko,Takemura, Yuki,Iwamoto, Ken-Ichi,Higashino, Takeo,Miyashita, Akira
, p. 199 - 206 (2007/10/03)
4-(α-Benzylα-hydroxybenzyl)quinazoline (4a) underwent retro-benzoin condensation catalyzed by cyanide ion to give deoxybenzoin (2a) and quinazoline (5a). Similarly, several nitrogen-containing heteroarenes (4, 9, 12, 16-19) having an α-hydroxybenzyl group at the α-position of the nitrogen underwent retro-benzoin type condensation to afford kelones (2) and heteroarenes (5). However, similar reaction of pyrazolopyrimidines (13, 14, 15) having an α-benzyl-α-hydroxybelzyl group resulted in benzyl migration, giving benzylpyrazolopyrimidines (8) and arenecarbaldehydes (3). Tetrabutylammonium cyanide (11, Bu4NCN) was a more effective cyanide ion donor than KCN (10). The retro-benzoin condensation was applied to the synthesis of 2-substituted quinazolines (38) from 2-chloro-4- aroylquinazolines (34), using the aroyl group as a protecting and electron- withdrawing group.
