Pergamon

Tetrahedron Letters, Vol. 37, No. 6, pp. 853-856,1996 Copyright© 1996Publishedby ElsevierSciencelad Printedin Great Britain.All rights reserved 0040-4039/96$15.00 + 0.00 0040-4039(95)02324-0

C/s-dioxomolybdenum(VI) Complexes as New Catalysts for the Meyer-Schuster Rearrangement.

Christian Y. Lorber and John A. Osborn*

Labom~ire de Chimie des M6lauxde Transitionet de Catalyse,as~ci6 au C.N.R.S., Universilt~Louis Pastet~, lnstitut Le Bel, 4 rue Blaise Pascal, 67000 Strasbourg,France.

Abstract: We describe a new catalytic system for the isomerisation of propargylic alcohols into ct,[3ethylenic carbonyl derivatives (Meyer-Schuster rearrangement) l, based on the combination of dioxomolybdenum(Vl)catalysts~mdsulfoxides,

The Meyer-Schuster rearrangement of a-acetylenic alcohols (scheme 1) leads to a,~-tmsaturated carbonyl compounds which are important organic intermediates, particularly in the synthesis of natural products of biological, pharmaceutical or cosmetic interest2,3 such as vitamin-A and its derivatives, terpens (for the synthesis of vitamins A, E, K, flavours and perfumes) and carotenoids.

Scheme 1

1~
R
HO

R~

Meyer-Schuster
,,

R2 R 3
I:11 O

Rearrangement

This rearrangement can been achieved by using a variety of catalysts such as strong acids which are unselective, 1,4 oxovanadium(V) complexes which need elevated temperatures, 5-7 MoO3 which needs also elevated temperatures (150-170°C) and gives only poor yields,5 n-B u4NReO4/p-TsOH which works at 25°C but is unselective (dehydration due to the presence of the acid), s and ziconium(IV) catalysts in association with CuC1. 9 To date, the best results were obtained using a catalytic system based on the couple Ti(OR)4/CuCI.10, tt In the present paper, we describe the use of molecular cis-dioxomolybdenum(VI) catalysts to isomerise propargylic alcohols. In contrast with oxovanadium catalysts, dioxomolybdenum(VI) complexes (5% mol) alone do not eatalyse the Meyer-Schuster rearrangement of 2-methyl 3-butyn 2-ol (methylbutynol), only incomplete conversion being observed in this case (see figure 1). However, when dimethylsulfoxide is used as solvent or cosolvent (ca 2 equiv DMSO/substrate), catalytic isomerisation takes place as shown in figure 1. Other sulfoxides, or pyridine-N-oxide, can as well serve as promoters (see table 1). Yet our best results 853

MoO2(NCS)4(PPh4)2 or even MoO 3.. followed by (2) formation of the allenyloxo complex ~ by a [3. MoO2(acac)2 1 equiv.12 Both ratesand seleedvities are further increased by ~altion of a catalytic amount of carhoxylic acid (compare entries 1 and 2). Figure 1: Isomerisafion of methylbutynol. 5 .) CH 3 H CH3 prenal O H 100°C methylbutynol (20 equiv. MoO2(acac)2 appears to give the highest isomerisation rate and selectivity. . The use of the same couple MoO2X2 / sulfoxide in the catalytic oxidation of alcohols will be presented elsewhere. 100°C. (1) formation of an alkynyloxo complex 1 by transesterification of the cis-dioxomolybdenum(VI) precursor. MoO2X2 (X = 1/2 acac.) 60' 50' 40' "~ 30' 20' 10 0 0 . (o) solvent : o-C6H4C12. This was also found for vanadium and titanium catalysts.. however. Complexes of type I could be isolated and characterised. 13 The general mechanism proposed5 for oxo-metal complex catalysed isomerisation of propargylic alcohols would appear to apply in part to the molybdenum(VI) catalysis reported here (scheme 2): i. is unsatisfactory for the rearrangement of primary and secondary alcohols. e. • . but compounds ~ have not been detected.9.g. C" CH3 / ~ HO MoO2(acac)2 (1 equiv. Such an effect has already been ~ e d in the isomerisation of propargylic alcohols catalysed by siloxovanadium 6a or titanium 7b catalysts. OAr or C1). The high selectivity obtained for methylbutynol is also found for other tertiary propargylic alcohols such as 3-methyl 1-pentyn 3-ol (entries 1-6). (*) solvent: o-C6H4C12 + 40 equiv.854 were obtained with dibutylsulfoxide (entries 1-3). since side-products resulting from the oxidation of the alcohol function are formed extensively (entries 9-10). liberating the allenol which rearrange to the product via a prototropic shift.3]-sigmatropic rearrangement (where the oxo ligands play a key role) via a metallacyclic intemzediate.(1:i) solvent : DMSO. A great range of molybdenum precursors can be used. • 10 15 20 25 Time (h) Conditions: methylbutynol 20 equiv. Whereas for more hindered alcohols like triphenylpropargylalcohol the reaction is very slow (entry 7).e. and then(S) alkoxide exchange occurs with a further molecule of substrate. The molybdenum catalyst. OR. DMSO.

[a] solvent: DMSO. $ selectivity = (yield]conversion)xl00.2X2 HaC~ / HaG " -XH H3C~"""~'/%O'~ H3CI~='~Hy HaCI~. Conditious Entry 1 2 3 4 5 6 Subswat¢# Promoter Bu2S=O Bu2S--O Ar'CO2HIbi Acid Temp.=tBuC6H4(5 equiv). q each product were first chancterised by GC-MS analysis. GC determination.'- O MoO.077 M). ? in %.. o-dichlorobvnzene2g (solvent).1] 30 lO[d] / OH H 9 CH3 I OH I I "~ ~ ell3 O H H ~ O = H Bu2S=O 100 5 CHa Cl-h~/ _.855 Table 1: CatalyticIsomefisationof Various Propargylic Alcohols. promoter 40 equiv.. HO { 0 H3C ~ ~N OH " r / 0 Mo%. [¢1mixtu~ of Z + E._.. [d] from oxidation of hydroxyl group. H 0 Conditions: Substrate 20 ¢quiv.(*c) Time (h) 100 I00 140 140 Ar'CO2HIb] Ar'CO2H[b] 100 100 5 5 0.5 1 5 5 Produed Yiddt 56 90 Sdectivity$ 92 99 98 75 99 99 CH3 OH i"~ H Bu2S=O DMSOla] Py-O GIla H CH3"~O 95 60 46 CH 3 T2 ~'~ OH Ph Ph I OH "--Ph H Bu2S=O CHa 0 Ph Ph /L. H 3C'#. ]/ .~J~ Pb H ~ C'zHsH 73[¢1 7 B u 2 S = O Ar'CO2H[b] 100 5 10 o 50 H 8 H I ~ ---CH a Bu2S=O 100 5 H H OH 3 O 18[¢1 9[. # Commercial products (Aldrich) except for entry 7. _ / OH II X~"M%0_4. Scheme 2: Catalytic cycle 14 I CH3 ~. [b] Ar. MoO2(acac)2 1 equiv (0.

G. 5. Lorber. S. 15. b) Yamano. 39 mg of MoO2(acac)2 (0. together with catalyst deactivation. Chem. S. 376-383 and references therein. Glenat. N. 11. Husama. Y. Tobe. 1971. 59. Ber. Babanyan.754 mmol). M. Y. K.. Mercier. Nota: X = OR.Chim. to be published.119 retool). W. 4.A. 156 nag of 4-tert-butylbenzoic acid (0. 10. the second oxo group serving as an active spectator ligand by stabilising the cyclic intermediate (or transition state). Chim. 1976. 429-438 and references therein. 3. Gulyi. 7. and a fraction of the propargylic alcohol is dehydrated into enyne. c) Heilman. Schuster. detector: FID): yield in prenal 90% (recovered alcohol: 9%). Tech (US) 1988. to be published. 150 mg of n-nonane (internal standard. Chem~ev. Thesis Universit6 Louis Pasteur de Strasbourg 1995. G. 6. 9. J. A. methylsilicon gum. M. Varagnat. J. 1. Chem. Acta 1976. I. Cheung.. The latter may serve to maintain molybdenum in oxidation state VI. G. 89-89. Keifits. M.. P. In the absence of promoter... L. N. the conversion is complete: yield in prenal 98%. 2. Sulfoxide ligands probably bound to molybdenum center are not represented in this scheme. Aul'Chenko. S. Lorber. 1994. E. J. Hindley. P. 200 mg of 2-methyl-3-butyn-2-ol (2. Osborn. V. H. 1922. 1994.. R. 59. Dulova... After 10 hours.. 33. the yield and selectivity were determined by gas chromatography (chromatograph: HP 5890 II. Tetrahedron Lett. 772 mg of dibutylsulfoxide (4. the isomerisation is only stoichiometric. Nugent. B.. 55. Perkin Trans. 1413-1416.. B. D. a) Swaminathan. G. S.53 mm x 2. Chem. 29. R. 13. Parshall. Narayanan. Youinou M. P. 1/2 acac . H. Y. E. a) Narasaka. Sac.2dichlorobenzene (solvent) were placed in a screw caps vial and heated to 100°C under stirring. I. Meyer. After 5 hours. C. 8.m. J. Mendeleev Commun. L. 8. b) Erman. CI. Andrews.. C. A.. 14. Acta 1976. Y. Helv.190 mmol) and 2 g of 1. 567-585. VorPin. 1991.594 mmol). Chim. R. 1967. Typical reaction conditions: Under an inert atmosphere. O. b) Vartayan.. Hayashi.. Osborn. 819-823.. appears to occur in its absence. C. column: HP-1. 1509-1518. E. D.. (Received in France 8 November 1995. Pure Appl. Tetrahedron 1977. accepted 4 December 1995) .Rev. C. Borer. Chem. V.. Helv.377 retool).. H.. Y.. K.. 10 m x 0.. 1233-1243.. a) Pauling. T. Chabard~s.1 1995. A. 34. 1963. 1775-1783..S... K. 1895-1904. since reduction to lower oxidation states.. References and Notes 1. Ito. Chabard~s. a) Erman. 66. Morgan. A. Tetrahedron Lett. 670-686. K. S..65 p.Chem. b) Olson. C.856 The presence of two oxo ligands on the catalyst may be at the origin of its relative efficiency.. Chem. A. 6253-6256. AurChenko. C. Saucy.. Y. 175-183.. Chabard~s. 12. Kuntz. Novikov. Lorber. 1988. Lett. Ann. 15 We are currently investigating in more detail the mechanism of the rearrangement mediated by these molybdenum catalysts. Russ. C. K. The role of the earboxylic acid and of the sulfoxide remains obscure. W. J. 2981-2984. H. M.