Asymmetric total syntheses of (+)-mycoepoxydiene and related natural product (-)-1893A: application of one-pot ring-opening/cross/ring-closing metathesis to construct their 9-oxabicyclo[4.2.1]nona-2,4-diene skeleton.
The total syntheses of (+)-mycoepoxydiene and (-)-1893A have been completed. The present synthetic strategy features the use of one-pot ring-opening/cross metathesis (ROM/CM) followed by a ring-closing metathesis (RCM) reaction, allowing for the concise construction of the 9-oxabicyclo[4.2.1]nona-2,4-diene framework from a 7-oxabicyclo[2.2.1]hept-2-ene derivative and 1,3-butadiene. The sequential metathesis product was converted into (+)-mycoepoxydiene through the oxidative rearrangement of a furfuryl alcohol to a pyranone, thereby establishing its absolute stereochemistry. From the common intermediate, a structurally related natural product (-)-1893A was also synthesized via the vinylogous aldol reaction.
Takao
Ken-ichi
K
Department of Applied Chemistry, Keio University, Hiyoshi, Kohoku-ku, Yokohama 223-8522, Japan.
Yasui
Hiroyuki
H
Yamamoto
Shun
S
Sasaki
Daisuke
D
Kawasaki
Soujiro
S
Watanabe
Gohshi
G
Tadano
Kin-ichi
K
D001952:Bridged-Ring Compounds / Q000138:chemical synthesis* / Q000737:chemistry*; D003516:Cycloparaffins / Q000138:chemical synthesis* / Q000737:chemistry*; D008968:Molecular Conformation; D011753:Pyrones / Q000138:chemical synthesis*
C496106:1893A compound; D001952:Bridged-Ring Compounds; D003516:Cycloparaffins; D011753:Pyrones; C476085:mycoepoxydiene