Synthesis of the aziridinomitosene skeleton by intramolecular Michael addition: alpha-lithioaziridines and nonaromatic substrates.
The bicyclic pyrrole ketone 16 has been prepared by using an oxaza-Claisen rearrangement, followed by nitrogen deprotection. Coupling with the stannylaziridine mesylate 15a or nosylate 15b affords 17. Conversion to 40 provides a substrate for generation of an alpha-lithioaziridine 41 by tin lithium exchange. An intramolecular Michael addition pathway for 41 has been demonstrated by the isolation of 46 in 20% yield under conditions where the intermediate enolate 43 is trapped by selenenylation, but competing proton transfer gives 42. The synthetic potential of the process is limited by stability problems at the stage of the enolate 43 or the protonated product 44.
Vedejs
Edwin
E
Chemistry Department, University of Wisconsin, Madison, WI 53706, USA. edved@umich.edu
Little
Jeremy D
JD
Seaney
Lisa M
LM
D000903:Antibiotics, Antineoplastic / Q000138:chemical synthesis*; D001388:Aziridines / Q000138:chemical synthesis*; D001643:Bridged Bicyclo Compounds / Q000737:chemistry; D003500:Cyclization; D003903:Deuterium; D007553:Isotope Labeling; D007659:Ketones / Q000737:chemistry; D008094:Lithium / Q000737:chemistry*; D008698:Mesylates / Q000737:chemistry; D011758:Pyrroles / Q000737:chemistry; D012643:Selenium / Q000737:chemistry; D013237:Stereoisomerism; D014001:Tin / Q000737:chemistry
D000903:Antibiotics, Antineoplastic; D001388:Aziridines; D001643:Bridged Bicyclo Compounds; D007659:Ketones; D008698:Mesylates; D011758:Pyrroles; C413848:aziridinomitosene; D014001:Tin; D008094:Lithium; D003903:Deuterium; D012643:Selenium