14058-54-9Relevant articles and documents
Rhodium-catalyzed cyclohydrocarbonylation: Application to the synthesis of (+)-prosopinine and (-)-deoxoprosophylline
Ojima, Iwao,Vidai, Ephraim S.
, p. 7999 - 8003 (1998)
Efficient convergent total syntheses of (+)-prosopinine (1) and (-)- deoxoprosophylline (4) were accomplished using Rh-BIPHEPHOS complex-catalyzed cyclohydrocarbonylation as the key step. The Rh-BIPHEPHOS complex-catalyzed cyclohydrocarbonylation of I, derived from (R)-serine, at 65 °C and 4 atm of CO and H2 (1:1) in ethanol afforded 6-ethoxypiperidine II, which was transformed to enantiopure (+)-prosopinine (1) in 3 steps. In a similar manner, (-)-deoxoprosophylline was synthesized through cyclohydrocarbonylation of IV derived from (S)-serine, giving 6- ethoxypiperidine V. The key intermediate V was transformed to enantiopure (- )-deoxoprosophylline (4) in 4 steps. These two short total syntheses clearly demonstrate the usefulness of the extremely regioselective cyclohydrocarbonylation process developed in these laboratories for the concise syntheses of piperidine alkaloids and related compounds.
Chiral and Stereoselective Total Synthesis of (-)-Deoxoprosopinine and (-)-Deoxopropsophylline. Intramolecular Aminomercuration of an ε,ζ-Unsaturated Amine
Saitoh, Yutaka,Moriyama, Yoshihiko,Hirota, Hiroshi,Takahashi, Takeyoshi,Khuong-huu, Qui
, p. 488 - 492 (1981)
L-Serine was transformed in 8 steps into (4R,5S)-2,2-dimethyl-4--1,3-dioxan-5-amine.This chiral ε,ζ-unsaturated amine was subjected to intramolecular aminomercuration and then acid hydrolysis to give (-)-deoxoprosopinine and (-)-deoxoprosophylline.
A concise and divergent approach to hydroxylated piperidine alkaloids and Azasugar Lactams
Guo, Lian-Dong,Liang, Pan,Zheng, Jian-Feng,Huang, Pei-Qiang
, p. 2230 - 2236 (2016/11/13)
The vinylogous Mannich reaction (VMR) between 2-(tertbutyldimethylsilyloxy) furan (TBSOF) and (RS)-t-BS-imine 12a and the application of the VMR adduct butenolide 13a as a versatile chiral building block for the synthesis of hydroxylated piperidine alkaloids and azasugars were investigated. Firstly, both the anti diastereoselectivity and the chemical yield of the asymmetric VMR between TBSOF and (RS)-t-BS-imine 12a were improved by the use of Sm(OTf)3/ H2O (1.5 equiv.) as the promoter. Similar diastereoselectivities were also obtained with Yb(OTf)3/H2O, Cu(OTf)2/H2O, Zn(OTf)2/H2O, or the Br?nsted acids TfOH or MsOH as the promotors. Secondly, an efficient four-step procedure for the elaboration of butenolide 13a into piperidine alkaloid (–)-deoxoprosophylline (2) was established. Thirdly, by taking advantage of the olefin functionality in the butenolide 13a, polyhydroxylated δ-lactams 23 and 21, which are ready precursors of azasugars L-deoxyallonojirimycin (ent-7) and L-3- epi-fagomine (ent-6), were obtained in two and three steps, respectively, via dihydroxylated lactone 17. The easily available synthetic intermediate 17 can also serve as a key intermediate for the synthesis of the glycosyl nucleoside amino acid cores of polyoxins and nikkomycins.
Synthesis of (-)-deoxoprosophylline, (+)-2- epi -deoxoprosopinine, and (2 R,3 R)- and (2 R,3 S)-3-hydroxypipecolic acids from d -glycals
Kokatla, Hari Prasad,Lahiri, Rima,Kancharla, Pavan K.,Doddi, Venkata Ramana,Vankar, Yashwant D.
experimental part, p. 4608 - 4611 (2010/09/30)
(Figure presented) New syntheses of (-)-deoxoprosophylline, (+)-2-epi-deoxoprosopinine, and (2R,3R)- and (2R,3S)-3-hydroxypipecolic acids are reported. Utilization of the chiral functionalities of Perlin aldehydes, derived from 3,4,6-tri-O-benzyl glycals,
