Process for the preparation of 6-alpha-hydroxy-N-alkylated opiates

A process for the preparation of a 6-keto morphinan having formula (I) prepared from a 6-keto nor-morphinan (X) having the formula:

• the process comprising reacting the 6-keto nor-morphinan (X) with an aldehyde of the formula CH(O)R9 in a solvent to form the 6-keto morphinan (I) having the formula:
• wherein
• R1 is hydrogen, hydrocarbyl, substituted hydrocarbyl, halo, or —OR111;
• R2 is hydrogen, hydrocarbyl, substituted hydrocarbyl, halo, or —OR211;
• R3 is hydrogen, hydrocarbyl, substituted hydrocarbyl, or —OR311;
• R7 is hydrogen, hydrocarbyl, substituted hydrocarbyl, or —OR711;
• R8 is hydrogen, hydrocarbyl, substituted hydrocarbyl, or —OR811;
• R9 is hydrogen, acyl, hydrocarbyl, substituted hydrocarbyl, or heterocyclo;
• R14 is hydrogen or hydroxy;
• R111 is hydrogen, hydrocarbyl, substituted hydrocarbyl, or a hydroxy protecting group;
• R211 is hydrogen, hydrocarbyl, substituted hydrocarbyl, or a hydroxy protecting group;
• R311 is hydrogen, hydrocarbyl, substituted hydrocarbyl, or a hydroxy protecting group;
• R711 is hydrogen, hydrocarbyl, substituted hydrocarbyl, or a hydroxy protecting group;
• R811 is hydrogen, hydrocarbyl, substituted hydrocarbyl, or a hydroxy protecting group;
• and
• Z1 is >N+═CH(R9).