650597-66-3Relevant articles and documents
A versatile catalyst system for enantioselective synthesis of 2-substituted 1,4-benzodioxanes
Chong, Eugene,Qu, Bo,Zhang, Yongda,Cannone, Zachary P.,Leung, Joyce C.,Tcyrulnikov, Sergei,Nguyen, Khoa D.,Haddad, Nizar,Biswas, Soumik,Hou, Xiaowen,Kaczanowska, Katarzyna,Chwalba, Micha?,Tracz, Andrzej,Czarnocki, Stefan,Song, Jinhua J.,Kozlowski, Marisa C.,Senanayake, Chris H.
, p. 4339 - 4345 (2019/04/17)
We report the synthesis of enantiomerically enriched 1,4-benzodioxanes containing alkyl, aryl, heteroaryl, and/or carbonyl substituents at the 2-position. The starting 1,4-benzodioxines were readily synthesized via ring closing metathesis using an efficient nitro-Grela catalyst at ppm levels. Excellent enantioselectivities of up to 99:1 er were obtained by using the versatile catalyst system [Ir(cod)Cl]2/BIDIME-dimer in the asymmetric hydrogenation of 2-substituted 1,4-benzodioxines. Furthermore, DFT calculations reveal that the selectivity of the process is controlled by the protonation step; and coordinating groups on the substrate may alter the interaction with the catalyst, resulting in a change in the facial selectivity.
From 2-aminomethyl-1,4-benzodioxane enantiomers to unichiral 2-cyano- and 2-carbonyl-substituted benzodioxanes via dichloroamine
Bolchi, Cristiano,Valoti, Ermanno,Straniero, Valentina,Ruggeri, Paola,Pallavicini, Marco
, p. 6732 - 6737 (2014/08/05)
2-Substituted 1,4-benzodioxanes, such as 2-cyano-, 2-methoxycarbonyl-, 2-aminocarbonyl-, and 2-formyl-1,4-benzodioxane, are key synthons that for the most part are never described as enantiomers or are inadequately characterized for enantiomeric purity. They were prepared by quantitative N,N-dichlorination of (R)- and (S)-2-aminomethyl-1,4-benzodioxane and successive functional group conversions in high yields without any racemization of the stereogenic benzodioxane C(2).
Chemoenzymatic synthesis of piperoxan, prosympal, dibozane, and doxazosin
Rouf, Abdul,Gupta, Pankaj,Aga, Mushtaq A.,Kumar, Brijesh,Chaubey, Asha,Parshad, Rajinder,Taneja, Subhash C.
, p. 1615 - 1623 (2013/02/22)
The synthesis of both enantiomers of 1,4-benzodioxan-2-carboxylic acid 1, a key synthetic intermediate for the therapeutic agents piperoxan, prosympal, dibozane, and doxazosin was achieved with good yields and high enantioselectivities via the Arthrobacter sp. lipase catalyzed kinetic resolution of ester (±)-17a. The influence of the co-solvents and the immobilization of the lipase upon kinetic resolution demonstrated that immobilized whole cells, in the presence of n-butanol as a co-solvent, resulted in the optimal resolution of the substrate (ee ~99%, E = 535) at 258 mmol (50 g/L) substrate concentration.