Enantioselective Total Synthesis of (+)-Arboridinine
- Resource Type
- Authors
- Hongbin Zhai; Bin Cheng; Zhen Zhang; Sujun Xie; Yun Li
- Source
- Journal of the American Chemical Society. 141(17)
- Subject
- Bicyclic molecule
Chemistry
Stereochemistry
Enantioselective synthesis
Total synthesis
General Chemistry
Alkylation
010402 general chemistry
01 natural sciences
Biochemistry
Catalysis
0104 chemical sciences
Stereocenter
Colloid and Surface Chemistry
Intramolecular force
Michael reaction
Moiety
- Language
- ISSN
- 1520-5126
The enantioselective total synthesis of cage-shaped alkaloid (+)-arboridinine is reported. The synthesis takes advantage of the stereoselective double-Mannich reaction to rapidly construct the aza[3.3.1]bicyclic core along with two quaternary stereocenters of the alkaloid. Key steps for the present synthesis include an enantioselective Michael addition establishing the original chiral center at C10 and intramolecular dearomative alkylation forging the cage-shaped ring system found in arboridinine, as well as creating the requisite quaternary carbon center at C3. The bridgehead hydroxyl moiety at C11 was installed through a late-stage cobalt-catalyzed decarboxylative acetoxylation reaction. This strategy enables a 14-step asymmetric total synthesis of (+)-arboridinine from the readily available starting materials with most of the transformations performed on the decagram scale.