The carbohydrate-sesquiterpene interface. directed synthetic routes to both (+)- and (-)-fomannosin from D-glucose
Paquette, LA; Peng, X; Yang, J; Kang, HJ
| HERO ID | 4923580 |
|---|---|
| In Press | No |
| Year | 2008 |
| Title | The carbohydrate-sesquiterpene interface. directed synthetic routes to both (+)- and (-)-fomannosin from D-glucose |
| Authors | Paquette, LA; Peng, X; Yang, J; Kang, HJ |
| Journal | Journal of Organic Chemistry |
| Volume | 73 |
| Issue | 12 |
| Page Numbers | 4548-4558 |
| Abstract | An enantiodivergent strategy for the total chemical synthesis of both naturally occurring (+)-fomannosin (1) and its (-)-antipode (ent-1) from alpha-D-glucose has been developed and successfully implemented. The key steps in the overall pathway include the following: (i) application of the zirconocene-mediated ring contraction of vinyl furanosides for the construction of highly substituted cyclobutanols; (ii) the use of ring-closing metathesis to form the pendant five-membered ring; (iii) making recourse to a monothio malonic ester to allow for chemoselective reduction to sensitive lactone intermediate 45; (iv) hydroxyl-directed dihydroxylation with OsO(4) to generate 48; and (v) sequential elimination via a cyclic sulfite and a cyclobutyl triflate. The bridge between the enantiomeric series consisted of a six-step linkup involving the structural modification of 22 so as to generate ent-30b. Optical activity was fully preserved throughout. |
| Doi | 10.1021/jo8004233 |
| Pmid | 18489155 |
| Wosid | WOS:000256757100023 |
| Is Certified Translation | No |
| Dupe Override | No |
| Is Public | Yes |
| Language Text | English |