Enantioselective construction of cis-2,6-disubstituted dihydropyrans: total synthesis of (-)-centrolobine.
This paper presents a simple and efficient route to chiral cis-6-substituted 2-(2-hydroxyethyl)-5,6-dihydro-2H-pyrans, a versatile chiral building block. The strategy is based on three key transformations: enantioselective hetero-Diels-Alder (HDA) reaction of aldehyde with Danishefsky's diene, selective reduction of carbonyl function, and Claisen or related rearrangement. The synthetic utility of the methodology is illustrated by total synthesis of antibiotic (-)-centolobine.
Chaładaj
Wojciech
W
Institute of Organic Chemistry, Polish Academy of Sciences, 01-224 Warsaw, Poland.
Kowalczyk
Rafał
R
Jurczak
Janusz
J
D000447:Aldehydes / Q000737:chemistry; D002384:Catalysis; D003500:Cyclization; D009682:Magnetic Resonance Spectroscopy; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry; D011714:Pyrans / Q000138:chemical synthesis* / Q000737:chemistry; D013237:Stereoisomerism; D013329:Structure-Activity Relationship
D000447:Aldehydes; D009942:Organometallic Compounds; D011714:Pyrans; C432457:centrolobin