Claims
- 1. A process for producing a stereoisomer of the compound of the formula: ##STR48## in the substantial absence of any other stereoisomer of said compound which comprises contacting an organometallic compound of the formula:
- ArMX
- with an optically active acyl halide, acyl amine or acid anhydride of the formula: ##STR49## wherein Ar is substituted or unsubstituted naphthyl, M is magnesium, R.sub.1 is methyl, X is halogen, Y is halogen, the group of the formula: ##STR50## wherein R' and R" are alkyl or aryl or when taken together with N form a heterocyclic moiety which optionally can contain other hetero atoms, or acyloxy, and Z is a protected hydroxy group or a sulfonyloxy group of the formula: ##STR51## wherein R.sub.2 is alkyl, cycloalkyl, alkenyl, alkynyl, aryl or arylalkyl.
- 2. A process for producing a material consisting essentially of a single stereoisomer of a compound of the formula: ##STR52## which comprises contacting an organometallic compound of the formula:
- ArMX
- with a material consisting essentially of a single stereoisomer of an acyl halide, acyl amine or acid anhydride of the formula: ##STR53## wherein Ar is substituted or unsubstituted naphthyl, M is magnesium, R.sub.1 is methyl, X is halogen, Y is halogen, the group of the formula: ##STR54## wherein R' and R" are alkyl or aryl or when taken together with N form a heterocyclic moiety which optionally can contain other hetero atoms, or acyloxy, and Z is a protected hydroxy group or a sulfonyloxy group of the formula: ##STR55## wherein R.sub.2 is alkyl, cycloalkyl, alkenyl, alkynyl, aryl or arylalkyl.
- 3. The process of claims 1, or 2 wherein Ar is 6-methoxy-2-naphthyl.
- 4. The process of claim 3 wherein Z is acetoxy, benzoyloxy, dihydropyranyloxy, trialkylsiloxy or a group of the formula: ##STR56## wherein R.sub.2 is alkyl, cycloalkyl, alkenyl, alkynyl, aryl or arylalkyl.
- 5. The process of claim 4 wherein Z is alkylsulfonyloxy.
- 6. The process of claim 4 wherein Z is methanesulfonyloxy.
- 7. The process of claim 4 wherein Z is arylsulfonyloxy.
- 8. The process of claim 4 wherein Z is benzenesulfonyloxy.
- 9. The process of claim 4 wherein Z is aralkylsulfonyloxy.
- 10. The process of claim 4 wherein Z is p-toluenesulfonyloxy.
- 11. A process for producing an .alpha.-arylalkanoic acid of the formula: ##STR57## which comprises: contacting an organometallic compound of the formula:
- ArMX, (Ar).sub.2 M or ArM'
- with an acyl halide, an acyl amine or an acid anhydride of the formula: ##STR58## wherein Ar is aryl, M is cadmium, copper(II), manganese, magnesium or zinc, M' is copper(I) or lithium, R.sub.1 is alkyl or cycloalkyl, X is halogen, Y is halogen, the group of the formula: ##STR59## wherein R' and R" are alkyl or aryl or when taken together with N form a heterocyclic moiety which optionally can contain other hetero atoms, or acyloxy, and Z is a protected hydroxy group or a sulfonyloxy group of the formula: ##STR60## wherein R.sup.2 is alkyl, cycloalkyl, alkenyl, alkynyl, aryl or arylalkyl to form a ketone of the formula: ##STR61## reducing said ketone to the corresponding alcohol; contacting said alcohol so formed with a protic or dipolar, aprotic solvent for a time sufficient to form the aldehyde of the formula: ##STR62## oxidizing said aldehyde to said acid, and if Z is a protected hydroxy group, converting said group to said sulfonyloxy group either before or after said reducing step but before said contacting step.
- 12. The process of claim 11 wherein said acyl halide, acyl amine or acid anhydride is optically active.
- 13. The process of claim 12 wherein Z is a group of the formula: ##STR63## wherein R.sub.2 is alkyl, cycloalkyl, alkenyl, alkynyl, aryl or aralkyl.
- 14. The process of claim 13 wherein Z is alkylsulfonyloxy.
- 15. The process of claim 13 wherein Z is methanesulfonyloxy.
- 16. The process of claim 13 wherein Z is arylsulfonyloxy.
- 17. The process of claim 13 wherein Z is benzenesulfonyloxy.
- 18. The process of claim 13 wherein Z is aralkylsulfonyloxy.
- 19. The process of claim 13 wherein Z is p-toluenesulfonyloxy.
- 20. The process of claims 11, 12, 13, 14, 15, 16, 17, 18 or 19 wherein said organometallic compound is ArMX in which M is magnesium and Ar is 6-methoxy-2-naphthyl, and R.sub.1 is methyl.
- 21. The process of claim 20 wherein said ketone is reduced with a borohydride reducing agent.
- 22. The process of claim 21 wherein said borohydride reducing agent is sodium borohydride.
- 23. The process of claim 20 wherein the rearrangement of said alcohol is effected in the presence of a protic or dipolar, aprotic solvent.
- 24. The process of claims 20 wherein said ketone is reduced with a borohydride reducing agent and said rearrangement is effected in the presence of a protic or dipolar, aprotic solvent.
Parent Case Info
This is a continuation of application Ser. No. 329,672, filed Dec. 11, 1981, abandoned.
US Referenced Citations (4)
Foreign Referenced Citations (1)
Number |
Date |
Country |
55-130934 |
Oct 1980 |
JPX |
Non-Patent Literature Citations (4)
Entry |
Kharasch, "Grignard Reactions of Nonmetallic Substances," pp. 709-766, 846-851 and 870-879 (1954). |
Cason, J. Am. Chem. Soc., 68, p. 2076 (1946). |
Milsow, J. Am. Chem. Soc., 75, pp. 2318-2322 (1953). |
Seebach, Angew. Chem. Internat. Ed., 7, pp. 619-621 (1968). |
Continuations (1)
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Number |
Date |
Country |
Parent |
329672 |
Dec 1981 |
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