(7R,8S,9S,12S)-1-Benz-yloxy-13,14-didehydro-12-hy-droxy-2,13-dimeth-oxy-N-methyl-morphinane.

In the title compound, C(26)H(31)NO(4), a sinomenine derivative, the angle between the two aromatic rings is 53.34 (4)°. The N-containing ring is in a chair conformation, while the other two non-planar rings are in a half-boat conformation. In the crystal, mol-ecules are linked by O-H⋯N inter-actions into a C(8) chain along [100].

(7R,8S,9S,12S)-1-(4-Chloro-benz-yloxy)-13,14-didehydro-12-hy-droxy-2,13-dimeth-oxy-N-methyl-morphinane.

The title compound, C(26)H(30)ClNO(4), a sinomenine derivative, has five six-membered rings, two of which are aromatic, with a dihedral angle of 34.13 (20)° between these. The N-containing ring and the fourth ring exhibit chair conformations, while the fifth ring approximates an envelope conformation. A single inter-molecular O-H⋯N hydrogen-bonding inter-action gives a one-dimensional chain structure which extends along the a axis. The absolute configuration for the mol-ecule has been determined.

(9S,13R,14S)-7,8-Didehydro-4-(4-fluoro-benz-yloxy)-3,7-dimeth-oxy-17-methyl-morphinan-6-one sesquihydrate.

In the title sinomenine derivative, C(26)H(28)FNO(4)·1.5H(2)O, the dihedral angle between the two aromatic rings is 55.32 (6)°. The N-containing ring has an approximate chair conformation, while other two rings have approximate envelope and half-chair conformations. One water mol-ecule is located on a twofold symmetry axis. In the crystal, the water mol-ecules form O-H⋯O and O-H⋯N hydrogen bonds, bridging symmetry-related main mol-ecules.

(8S,9S,10R)-4-(4-Chloro-benz-yloxy)-7,8-didehydro-3,7-dimeth-oxy-17-methyl-morphinan-6-one monohydrate.

In the title compound, C(26)H(28)Cl(N)O(4)·H(2)O, the dihedral angle betwene the two aromatic rings is 69.73 (6)°. The N-containing ring exhibits a chair conformation, while the other non-aromatic rings are in approximate envelope conformations. In the crystal, the water mol-ecule forms O-H⋯O and O-H⋯N hydrogen bonds and a C-H⋯O link also occurs.

Chiral N-heterocyclic carbene catalyzed annulation of α,ß-unsaturated aldehydes with 1,3-dicarbonyls.

Chiral N-heterocyclic carbene catalyzed annulations of ynals and enals with 1,3-dicarbonyls have been described. The two reactions provided direct and efficient methods for enantioselective synthesis of functionalized dihydropyranones. Comparatively, the reactions starting from ynals were atom-economical; furthermore the reactions of enals demonstrated broader substrate compatibility.

(9S,13R,14S)-7,8-Didehydro-4-(4-iodo-benz-yloxy)-3,7-dimeth-oxy-17-methyl-morphinan-6-one monohydrate.

In the title compound, C(26)H(28)INO(4)·H(2)O, benzene rings are inclined at a dihedral angle of 69.9 (1)°. The N-containing ring exhibits a chair conformation, while the other rings approximate to envelope conformations. In the crystal, the uncoordinated water mol-ecule forms inter-molecular O-H⋯O and O-H⋯N hydrogen bonds.