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DOI: 10.1055/s-2003-43370
Alkylative Reduction of Titanium(IV) Isopropoxide with EtMgBr: Convenient Method for the Generation of Subvalent Titanium Alkoxide Reagents and their Reactivity in Pinacol Coupling Reactions
Publication History
Publication Date:
26 November 2003 (online)
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Abstract
The composition of the gaseous products from the reaction of Ti(IV) isopropoxide with ethylmagnesium bromide in diethyl ether evidences the formation of subvalent titanium isopropoxide species in various oxidation states depending on relative amounts of the reactants. Reaction of titanium(IV) isopropoxide with one equivalent of the Grignard reagent gives presumably titanium(III) isopropoxide. The latter is generated as a result of disproportionation of starting Ti(IV) species and titanium(II) isopropoxide-ethene complex which is formed as a result of ethane extrusion from diethyltitanium(IV) isopropoxide. Titanium(III) isopropoxide prepared by this way transforms the aldehydes and the aromatic ketones into the corresponding pinacols in good yields.
Key words
titanium compounds - reduction - Grignard reagents - carbonyl compounds - pinacol coupling
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1a
Kulinkovich OG.Sviridov SV.Vasilevskii DA.Pritytskaya TS. J. Org. Chem. USSR (Engl. Transl.) 1989, 25: 2027 -
1b
Kulinkovich OG.Sviridov SV.Vasilevskii DA. Synthesis 1991, 234 - 2
Epstein OL.Savchenko AI.Kulinkovich OG. Russ. Chem. Bull. 2000, 278 - For reviews see:
-
3a
Kulinkovich OG. Chem. Rev. 2003, 103: 2597 -
3b
Kulinkovich OG.de Meijere A. Chem. Rev. 2000, 100: 2789 -
4a
Kulinkovich OG.Savchenko AI.Sviridov SV.Vasilevsky DA. Mendeleev Commun. 1993, 230 -
4b
Epstein OL.Savchenko AI.Kulinkovich OG. Tetrahedron Lett. 1999, 40: 5935 -
5a
Eisch JJ.Gitua JN.Otieno PO.Shi X. J. Organomet. Chem. 2001, 624: 229 -
5b
Eisch JJ.Gitua JN. Organometallics 2003, 22: 24 - 6 For physical and spectral data on monomeric (t-Bu3SiO)3Ti, see:
Covert KJ.Wolchanski PT.Hill SA.Krusic PJ. Inorg. Chem. 1992, 31: 66 - For physical and spectral data on dimeric aryloxide derivative [(2,6-Ph2C6H3O)2TiCl]2, see:
-
7a
Thorn MG.Hill JE.Waratuke SA.Johnson ES.Fanwick PE.Rothwell IP. J. Am. Chem. Soc. 1997, 119: 8630 -
7b
Hill JE.Fanwick PE.Rothwell IP. Polyhedron 1990, 9: 1617 - 8 For a recent review, see:
Gansäuer A.Bluhm H. Chem. Rev. 2000, 100: 2771 ; and references therein - 13
Trahanovsky WS.Gilmore JR.Heaton PC. J. Org. Chem. 1973, 38: 760 -
14a
Cram DJ.Kopecky KR. J. Am. Chem. Soc. 1959, 81: 2748 -
14b
Fürstner A.Csuk R.Rohrer Ch.Weidmann H. J. Chem. Soc., Perkin Trans. 1 1988, 1729 - 15
Criegee R.Höger E.Huber G.Kruck P.Marktscheffel F.Schellenberger H. Liebigs Ann. Chem. 1956, 599: 6
References
Procedure for Pinacol Coupling: To a solution of Ti(i-PrO)4 (2.05 g, 7.3 mmol) in THF (6 mL) under argon atmosphere, a solution of EtMgBr prepared from Mg (0.19 g, 7.9 mmol) and EtBr (0.9 g, 8.2 mmol) in THF (8 mL) was added for a 2 min. The initially colorless solution turned blue, green-brown and black-brown over the course of EtMgBr addition. The reaction mixture was stirred and refluxed for 30 min under argon, then a solution of carbonyl compound in THF (2 mL) was added in one portion at r.t. or at reflux. The reaction mixture was stirred for a denoted time (Table [2] ) and then diluted with 20 mL of Et2O and quenched with 20 mL of 10% H2SO4 (in the case of the example in entry 5 the reaction mixture was quenched with aq NH4CI and filtered). Organic layer was separated, washed with H2O, aq NaHCO3 and dried over MgSO4. After removing of the solvent in vacuo the resulting reaction mixtures were analyzed by 1H NMR and then crystallized from CCI4 or EtOH.
10The treatment of benzophenone with 1 equiv of Ti(II) isopropoxide, prepared by alkylative reduction of Ti(IV) isopropoxide with EtMgBr in THF at r.t., led to 39% of pinacol 8, 3% of benzhydrol 9, and 47% of the starting compound was recovered.
11The treatment of benzophenone with 1 equiv of Ti(II) isopropoxide, prepared by alkylative reduction of Ti(IV) isopropoxide with EtMgBr in THF at -78 °C, led to 58% of pinacol 8, 1% of benzhydrol 9, and 21% of the starting compound was recovered.
12Selected NMR data for pinacol coupling products:
dl
- and meso
-1,2-bis(4′-Chlorophenyl)ethane-1,2-diol. 1H NMR (lit.
[13]
) (400 MHz, CDCI3), dl: δ = 2.93 (s, 2 H, OH), 4.61 (s, 2 H, CH), 7.00 (d, 4 H, J = 8.6 Hz), 7.20 (d, 4 H, J = 8.6 Hz); meso: δ = 2.36 (s, 2 H, OH), 4.83 (s, 2 H, CH), 7.09 (d, 4 H, J = 8.6 Hz), 7.25 (d, 4 H, J = 8.6 Hz).
dl
- and meso
-2,3-Diphenylbutane-2,3-diol. 1H NMR (lit.
[14]
) (400 MHz, CDCI3), dl: δ = 1.50 (s, 6 H, CH3), 2.59 (s, 2 H, OH), 7.17-7.26 (m, 10 H, Ph-H); meso: δ = 1.58 (s, 6 H, CH3), 2.29 (s, 2 H, OH), 7.17-7.26 (m, 10 H, Ph-H).
dl
- and meso
-Dodecane-6,7-diol.
[15]
1H NMR (400 MHz, CDCI3), dl: δ = 0.85-0.93 (m, 6 H, CH3), 1.21-1.54 (m, 16 H, CH2), 1.92-2.05 (s, 2 H, OH), 3.37-3.41 (m, 2 H, CH); meso: δ = 0.85-0.93 (m, 6 H, CH3), 1.21-1.54 (m, 16 H, CH2), 1.92-2.05 (s, 2 H, OH), 3.57-3.63 (m, 2 H, CH).