NOVELTY - Preparation of saturated ketone morphinan compound (I) involves contacting (1S,5R,13R)-12-oxa-4-azapentacyclo(9.6.1.01,13.05,17.07,18)octadeca-7(18),8,10,15-tetraene-10,14-diol (II) with rhodium complex, and organic additive chosen from alcohol (IIIa), ketone (IIIb), ether (IIIc) and thioether (IIId).    USE - Preparation of saturated ketone morphinan compound used for preparing pharmaceutical formulation (claimed) used as opioid receptor modulator.    ADVANTAGE - The method is economical, efficient and environmentally-friendly, and enables preparation of highly-pure saturated ketone morphinan compound with high yield, using less amount of solvents and reagents.    DETAILED DESCRIPTION - Preparation of saturated ketone morphinan compound of formula (I) involves contacting (1S,5R,13R)-12-oxa-4-azapentacyclo(9.6.1.01,13.05,17.07,18)octadeca-7(18),8,10,15-tetraene-10,14-diol of formula (II) with rhodium complex, and organic additive chosen from alcohol of formula (IIIa), ketone of formula (IIIb), ether of formula (IIIc) and thioether of formula (IIId).    R1=1-18C alkyl, 2-18C alkenyl, 2-18C alkynyl or 3-18C cycloalkyl (all optionally substituted by halo or hydroxy protecting group), or H;    R2=1-18C alkyl, 2-18C alkenyl, 2-18C alkynyl or 3-18C cycloalkyl (all optionally substituted by halo or nitrogen protecting group), or H;    R3=1-18C alkyl, 1-18C alkoxy, 2-18C alkenyl, 2-8C alkynyl or 3-18C cycloalkyl (all optionally substituted by halo or -OR'), H or -OH;    R'=hydroxy protecting group;    R4=R1;    R5=R2;    R6=R3;    R7-R9=1-6C alkyl, 2-6C alkenyl, aryl or hetero aryl (all optionally substituted by halo or 1-4C alkyl), or H;    or at least two of R7-R9+C=4- or 8-membered cyclic alcohol optionally containing one or more unsaturated bonds within the ring, and optionally substituted by one or more halo or 1-4C alkyl;    R10,R11=1-4C alkyl, 2-4C alkenyl, aryl or hetero aryl (all optionally substituted by halo or 1-4C alkyl);    R10+R11+C=4- or 8-membered cyclic ketone optionally containing one or more unsaturated bonds within the ring, and optionally substituted by one or more halo or 1-4C alkyl;    R12,R13=1-4C alkyl or 2-4C alkenyl (both optionally substituted by halo or 1-4C alkyl);and    R12+R13+C=4- or 7-membered cyclic thioether optionally containing one or more unsaturated bonds within the ring, and ring is optionally substituted by one or more halo or 1-4C alkyl.    INDEPENDENT CLAIMS are included for the following:    (1) preparation of salt of saturated ketone morphinan compound (I), which involves preparing saturated ketone morphinan compound (I), optionally isolating and/or purifying the compound (I), and associating the obtained compound with organic acid which is tartaric acid;    (2) preparation of pharmaceutical formulation, which involves associating the salt of saturated ketone morphinan compound (I) with excipients, adjuvants, diluents or carriers; and    (3) hydrocodone product, which comprises less than 10 ppm codeinone. At least portion of the codeinone is derived from transition metal mediated redox summarization of codeine to hydrocodone.