Transannular macrocyclization via intramolecular B-alkyl Suzuki reaction.
[reaction: see text]Transannular macrocyclizations via intramolecular B-alkyl Suzuki reactions are described. Regioselective terminal olefin hydroboration with 9-BBN followed by Pd(0)-catalyzed Suzuki reaction in the presence of a base such as TlOEt at high dilution generates macrocycles with a high degree of control over olefin geometry with isomerically pure E or Z vinyl iodide substrates. These reactions are complementary to ring closing metathesis (RCM) macrocyclizations and may prove superior in cases where control of olefin geometry is required.
Chemler
S R
SR
Department of Bioorganic Chemistry, Sloan-Kettering Institute for Cancer Research, New York, New York 10021, USA.
Danishefsky
S J
SJ
D001952:Bridged-Ring Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D002586:Cesium; D002625:Chemistry, Organic; D003500:Cyclization; D007202:Indicators and Reagents; D007659:Ketones; D055601:Organic Chemistry Phenomena
D001952:Bridged-Ring Compounds; D007202:Indicators and Reagents; D007659:Ketones; D002586:Cesium