Synthesis of the tetracyclic core of exiguaquinol.
A Diels-Alder reaction, a desymmetrizing aldol reaction, and a reductive Heck cyclization are employed in a short synthesis of a tetracycle relevant to exiguaquinol, a potential antibiotic. Ground-state energies of this advanced model system and the natural product rationalize the incorrect hemiaminal configuration experimentally obtained and point to the importance of the sulfonate in dictating the relative configuration of the natural product.
Department of Chemistry, University of California , 1102 Natural Sciences II, Irvine, California 92697-2025, United States , and Department of Chemistry and Biochemistry, University of California , Los Angeles, California 90095-1569, United States.
Gregg M
GM
Schwarzwalder
Sarah E
SE
Steinhardt
Hung V
HV
Pham
K N
KN
Houk
Christopher D
CD
Vanderwal
D000447:Aldehydes; D018360:Crystallography, X-Ray; D003500:Cyclization; D061565:Cycloaddition Reaction; D016480:Helicobacter pylori / Q000187:drug effects / Q000201:enzymology; D006873:Hydroquinones / Q000138:chemical synthesis* / Q000737:chemistry; D015394:Molecular Structure; D019906:Nuclear Magnetic Resonance, Biomolecular; D013237:Stereoisomerism
D000447:Aldehydes; D006873:Hydroquinones; C530467:exiguaquinol; C116609:3-hydroxybutanal