Methods for preparing isotopically modified 1,4-diene systems from non-isotopically modified 1,4-dienes involve selective oxidation of one or more bis-allylic position(s), or the preparation of isotopically modified 1,4-diene systems via trapping pi-allylic complexes with a source of deuterium or tritium. Such methods are useful for preparing isotopically modified polyunsaturated lipid including polyunsaturated fatty acids and polyunsaturated fatty acid derivatives.

Methods for preparing isotopically modified 1,4-diene systems from non-isotopically modified 1,4-dienes involve selective oxidation of one or more bis-allylic position(s), or the preparation of isotopically modified 1,4-diene systems via trapping pi-allylic complexes with a source of deuterium or tritium. Such methods are useful for preparing isotopically modified polyunsaturated lipid including polyunsaturated fatty acids and polyunsaturated fatty acid derivatives.

The present invention provides a compound having a dihydropyran structure, a method of producing a compound having a dihydropyran structure, a method of producing Pre-SMTP, a method of producing a group of SMTPs, and a pharmaceutical composition. The compound having a dihydropyran structure can be a useful intermediate in the chemically producing a group of Pre-SMTP and SMTP. Specifically, the compound having a dihydropyran structure is represented by the following formula (1), wherein: R.sub.3Si is a silyl group selected from TMS: trimethylsilyl, TES: triethysilyl, TBS (TBDMS): tert-butyldimethylsil, TIPS: triisopropylsilyl, TBDPS: tert-butyldiphenylsilyl, X is selected from COOH, CHO, and —CH═C(CH.sub.3)—(CH.sub.2).sub.2—CH═C(CH.sub.3).sub.2. ##STR00001##

The present invention provides a compound having a dihydropyran structure, a method of producing a compound having a dihydropyran structure, a method of producing Pre-SMTP, a method of producing a group of SMTPs, and a pharmaceutical composition. The compound having a dihydropyran structure can be a useful intermediate in the chemically producing a group of Pre-SMTP and SMTP. Specifically, the compound having a dihydropyran structure is represented by the following formula (1), wherein: R.sub.3Si is a silyl group selected from TMS: trimethylsilyl, TES: triethysilyl, TBS (TBDMS): tert-butyldimethylsil, TIPS: triisopropylsilyl, TBDPS: tert-butyldiphenylsilyl, X is selected from COOH, CHO, and —CH═C(CH.sub.3)—(CH.sub.2).sub.2—CH═C(CH.sub.3).sub.2. ##STR00001##

A method of reducing an aromatic ring or a cyclic, allylic ether in a compound includes preparing a reaction mixture including a compound including an aromatic moiety or a cyclic, allylic ether moiety, an alkali metal, and either ethylenediamine, diethylenetriamine, triethylenetetramine, or a combination thereof, in an ether solvent; and reacting the reaction mixture at from −20° C. to 30° C. for a time sufficient to reduce a double bond in the aromatic moiety to a single bond or to reduce the cyclic, allylic ether moiety.

A method of reducing an aromatic ring or a cyclic, allylic ether in a compound includes preparing a reaction mixture including a compound including an aromatic moiety or a cyclic, allylic ether moiety, an alkali metal, and either ethylenediamine, diethylenetriamine, triethylenetetramine, or a combination thereof, in an ether solvent; and reacting the reaction mixture at from −20° C. to 30° C. for a time sufficient to reduce a double bond in the aromatic moiety to a single bond or to reduce the cyclic, allylic ether moiety.

Methods for preparing isotopically modified 1,4-diene systems from non-isotopically modified 1,4-dienes involve selective oxidation of one or more bis-allylic position(s), or the preparation of isotopically modified 1,4-diene systems via trapping pi-allylic complexes with a source of deuterium or tritium. Such methods are useful for preparing isotopically modified polyunsaturated lipid including polyunsaturated fatty acids and polyunsaturated fatty acid derivatives.

Methods for preparing isotopically modified 1,4-diene systems from non-isotopically modified 1,4-dienes involve selective oxidation of one or more bis-allylic position(s), or the preparation of isotopically modified 1,4-diene systems via trapping pi-allylic complexes with a source of deuterium or tritium. Such methods are useful for preparing isotopically modified polyunsaturated lipid including polyunsaturated fatty acids and polyunsaturated fatty acid derivatives.

Methods for preparing isotopically modified 1,4-diene systems from non-isotopically modified 1,4-dienes involve selective oxidation of one or more bis-allylic position(s), or the preparation of isotopically modified 1,4-diene systems via trapping pi-allylic complexes with a source of deuterium or tritium. Such methods are useful for preparing isotopically modified polyunsaturated lipid including polyunsaturated fatty acids and polyunsaturated fatty acid derivatives.

The invention comprises novel chiral metal complex compounds of the formula ##STR00001## wherein M, PR.sup.2, R.sup.3 and R.sup.4 are outlined in the description, its stereoisomers, in the form as a neutral complex or a complex cation with a suitable counter ion. The chiral metal complex compounds can be used in asymmetric reactions, particularly in asymmetric reductions of ketones, imines or oximes.