Enantiocontrolled synthesis of highly functionalized tropanes via [5 + 2] cycloaddition to eta(3)-pyridinylmolybdenum pi-complexes.
[reaction: see text] A chiral, nonracemic eta(3)-pyridinyl scaffold participates in [5 + 2] cycloaddition with electron-deficient alkenes, an allene, and an alkyne to give eta(3)-allylmolybdenum bicyclic adducts. The adducts can be demetalated, providing a convergent route to highly functionalized tropanes. High enantiocontrol can be achieved throughout the cycloaddition and demetalation sequence.
Malinakova
H C
HC
Sanford S. Atwood Chemistry Center, Emory University, 1515 Pierce Drive, Atlanta, Georgia 30322, USA.
Liebeskind
L S
LS
D000475:Alkenes / Q000737:chemistry; D000480:Alkynes / Q000737:chemistry; D018360:Crystallography, X-Ray; D003500:Cyclization; D008982:Molybdenum; D009942:Organometallic Compounds / Q000737:chemistry*; D011725:Pyridines / Q000737:chemistry*; D013237:Stereoisomerism; D014326:Tropanes / Q000138:chemical synthesis*
D000475:Alkenes; D000480:Alkynes; D009942:Organometallic Compounds; D011725:Pyridines; D014326:Tropanes; D008982:Molybdenum