Tandem Intramolecular Benzyne-Furan Cycloadditions. Total Synthesis of Vineomycinone B(2) Methyl Ester.

Tetrahedron
Steven M SparksStephen F Martin

Abstract

We have exploited tandem intramolecular benzyne-furan cycloadditions employing three different benzyne precursors to generate substituted bisoxabenzonorbornadienes in a single operation. The regiochemical outcomes in these Diels-Alder reactions were effectively controlled by using disposable silicon tethers to link the reacting benzynes and furan moieties. Two different methods for converting the intermediate bisoxabenzonorbornadienes to substituted anthrarufins were developed. The first tactic entails the initial cleavage of the silicon tethers followed by regioselective ring opening of the oxabicycloheptadienes and oxidation of the central ring giving the target anthrarufin, whereas the second features the regioselective ring opening of the oxabicycloheptadienes followed by protiodesilylation and oxidation. When the starting furans bear carbohydrate substitutents, this new methodology enables the rapid assembly of the glycosyl-substituted aromatic cores of complex C-aryl glycoside antibiotics from simple starting materials. The utility of this novel approach to anthrarufins and C-aryl glycosides is exemplified in a triply convergent synthesis of vineomycinone B(2) methyl ester.

References

Jul 1, 1987·The British Journal of Dermatology·G C Priestley
Jun 1, 1987·Natural Product Reports·J C Vederas
Nov 1, 1970·Tetrahedron·M SezakiM Ono
May 1, 1982·The Journal of Antibiotics·N ImamuraS Omura
Oct 1, 1981·The Journal of Antibiotics·H OkazakiT Kishi
Nov 1, 1981·The Journal of Antibiotics·N ImamuraS Omura
Dec 1, 1995·The Journal of Antibiotics·N KawamuraT Takeuchi
Jul 13, 2001·Journal of the American Chemical Society·D E KaelinS F Martin
Oct 23, 2003·Journal of the American Chemical Society·David E KaelinStephen F Martin
Sep 25, 2004·Organic Letters·Chi-Li Chen, Stephen F Martin
Oct 19, 2006·Journal of the American Chemical Society·Chi-Li ChenStephen F Martin

❮ Previous
Next ❯

Citations

Oct 19, 2013·Organic & Biomolecular Chemistry·Robert L RaeMagnus W P Bebbington
Oct 21, 2010·Journal of the American Chemical Society·B Michael O'KeefeStephen F Martin
Oct 1, 2014·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Justyna M ZurekMagnus W P Bebbington
Feb 15, 2014·Journal of the American Chemical Society·Adam E GoetzNeil K Garg
Aug 8, 2015·Chemistry : a European Journal·Hem Raj KhatriJianglong Zhu
Mar 27, 2012·Chemical Reviews·Pamela M Tadross, Brian M Stoltz
Dec 14, 2011·Organic Letters·Abdelatif ElMarrouniJanine Cossy
Jul 25, 2017·The Journal of Organic Chemistry·Stephen F Martin
Oct 26, 2018·Chemical Society Reviews·Hiroshi TakikawaKeisuke Suzuki
Nov 19, 2010·Organic Letters·Kristen J ProckoStephen F Martin
Sep 16, 2017·Chemical Reviews·You Yang, Biao Yu
Dec 28, 2017·Chemical Reviews·Kei KitamuraKeisuke Suzuki

❮ Previous
Next ❯

Related Concepts

Related Feeds

Antifungals

An antifungal, also known as an antimycotic medication, is a pharmaceutical fungicide or fungistatic used to treat and prevent mycosis such as athlete's foot, ringworm, candidiasis, cryptococcal meningitis, and others. Discover the latest research on antifungals here.

Cardiac Glycosides

Cardiac glycosides are a diverse family of naturally derived compounds that bind to and inhibit na+/k+-atpase. Discover the latest research on cardiac glycosides heres.

Antifungals (ASM)

An antifungal, also known as an antimycotic medication, is a pharmaceutical fungicide or fungistatic used to treat and prevent mycosis such as athlete's foot, ringworm, candidiasis, cryptococcal meningitis, and others. Discover the latest research on antifungals here.