- Programmed serial stereochemical relay and its application in the synthesis of morphinans
-
Herein we report a rationally designed, serial point-to-axial and axial-to-point stereoinduction and its integration into multi-step and target-oriented organic synthesis. In this proof-of-concept study, the configurational stability of several carefully designed atropisomeric intermediates and the fidelity of their unconventional stereoinductions were systematically investigated. The highly functionalized prepared synthetic intermediate was further applied in a novel chemical method to access the morphinans and it is potentially applicable to other structurally related alkaloids.
- Park, Kun Ho,Chen, Rui,Chen, David Y.-K.
-
p. 7031 - 7037
(2017/10/05)
-
- Biotransformations of morphine alkaloids by fungi: N-demethylations, oxidations, and reductions
-
Morphine alkaloids and some of its derivatives (morphine, codeine, thebaine, oripavine, hydrocodone, and oxycodone) were subjected to fermentations with six fungal strains. The alkaloids were transformed to a variety of products via biological oxidations, reductions, and oxidative demethylations. The strain Cunninghamella echinulata proved to be the most effective for demethylations of all of the above compounds, except for morphine. The time profile of the conversion of 3-[14CH3]thebaine to 3-[ 14CH3]northebaine by C. echinulata cultures was also determined.
- Chaudhary, Vigi,Leisch, Hannes,Moudra, Alena,Allen, Blake,De Luca, Vincenzo,Cox, D. Phillip,Hudlicky, Tomas
-
experimental part
p. 1179 - 1193
(2010/04/26)
-
- Enantioselective synthesis of (-)-dihydrocodeinone: A short formal synthesis of (-)-morphine
-
The radical cyclization approach to the morphine alkaloids has been applied in an asymmetric synthesis of (-)-dihydrocodeinone. A chiral cyclohexenol (R-32), from the CBS reduction of the enone, is the source of chirality. The first key step, tandem closure in which stereochemistry is controlled by geometric constraints, (-)-15b → (+)-16, was followed by an unprecedented reductive hydroamination, completing the synthesis of (-)-dihydroisocodeine ((-)-17) in 13 steps from commercially available materials.
- Parker, Kathlyn A.,Fokas, Demosthenes
-
p. 449 - 455
(2007/10/03)
-