Combined directed ortho metalation-halogen dance (HD) synthetic strategies. HD-anionic ortho fries rearrangement and double HD sequences.
A general and efficient directed ortho metalation (DoM)-halogen dance (HD)-electrophile quench sequence for the synthesis of trisubstituted pyridyl O-carbamates is described. A second HD sequence furnishes highly functionalized tetrasubstituted pyridines. Furthermore, a hitherto unobserved double HD rearrangement is reported. Under similar LDA conditions, aromatic O-carbamates with OMe, Cl, and F substituents (4a-c) undergo either a HD-electrophile quench sequence, 4a-c --> 18-20, or a HD-anionic ortho Fries rearrangement, 4a-c --> 6a-c, respectively.
Miller
Ricarda E
RE
Fachbereich Chemie and Konstanz Research School of Chemical Biology, Universität Konstanz, Fach 720, D-78457 Konstanz, Germany.
Rantanen
Toni
T
Ogilvie
Kevin A
KA
Groth
Ulrich
U
Snieckus
Victor
V
D002219:Carbamates / Q000138:chemical synthesis* / Q000737:chemistry; D015394:Molecular Structure; D013237:Stereoisomerism
D002219:Carbamates