Reaktion #2393463

ord-9f99d539fa9b4cdb967d68b25f671f68

Reaktionsgleichung

mCPBA

$C/C(=C\c1csc(C)n1)[C@@H]1C[C@@H]2O[C@@H]2CCC[C@H](C)[C@H](O)[C@@H](C)C(=O)C(C)(C)[C@@H](O)CC(=O)O1$

epothilone A

→

$C/C(=C\c1csc(C)n1)[C@@H]1C[C@@H]2O[C@@H]2CCC[C@H](C)[C@H](O)[C@@H](C)C(=O)C(C)(C)[C@@H](O)CC(=O)O1$

Ausbeute 50.0%

$C/C(=C\c1csc(C)n1)[C@@H]1C[C@@H]2O[C@@H]2CCC[C@H](C)[C@H](O)[C@@H](C)C(=O)C(C)(C)[C@@H](O)CC(=O)O1$

epothilone A

Ausbeute 50.0%

dimethyldioxirane

Edukte

$C/C(=C\c1csc(C)n1)[C@@H]1C[C@@H]2O[C@@H]2CCC[C@H](C)[C@H](O)[C@@H](C)C(=O)C(C)(C)[C@@H](O)CC(=O)O1$

epothilone A

—

Reagenzien

Keine

Reaktionsbedingungen

Detaillierte Bedingungen

See reaction.notes.procedure_details.

Aufarbeitung

1
Sonstigegave a different product distribution

Vorschrift

The cis-olefin 49 was converted to epothilone A (1) by the action of mCPBA (0.8-1.2 equivalents) in a reaction that, in addition to 1 (35% yield), produced the isomeric epoxides 51 (13% yield), 52 (or 53) (9% yield, stereochemistry unassigned) and 53 (or 52) (7% yield, stereochemistry unassigned), as well as bis(epoxides) 54 (or 55) and 55 (or 54) (10% total yield, stereochemistry unassigned). Reaction of olefin 49 with excess mCPBA (1.3-2.0 equivalents) gave a different product distribution: 1 (15%), 51 (10%), 52 (or 53) (10%), 53 (or 52) (8%), 54 (or 55) (8%), 55 (or 54) (7%), 56 (5%), and 57 (5%). The action of dimethyldioxirane (Murray et al. J. Org. Chem. 1985, 50, 2847-2853) (Methylene chloride, 0° C.) on 49 gave mainly 1 (50%) and 51 (15%), together with small amounts of 53 (or 54) and 54 (or 53) (10% total yield).

Quelle

DOI: 10.6084/m9.figshare.5104873.v1Patent: US06441186B1uspto-grants-2002_08