A New and Selective Metal-Catalyzed Baeyer-Villiger Oxidation Procedure

Synlett

Volumn 1997, Issue 8, 1997, Pages 971-973

  Göttlich, Richard ^a   Yamakoshi, Koichi ^a   Sasai, Hiroaki ^a   Shibasaki, Masakatsu ^a  

^a UNIVERSITY OF TOKYO   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0041620889     PISSN: 09365214     EISSN: None     Source Type: Journal    
DOI: 10.1055/s-1997-966     Document Type: Article

References (21)

1. For reviews on the Baeyer-Villiger reaction see: Hassall, C. Org. React. 1957, 9, 73. Krow, G. R. Org. React. 1993, 43, 3.
2. For reviews on the Baeyer-Villiger reaction see: Hassall, C. Org. React. 1957, 9, 73. Krow, G. R. Org. React. 1993, 43, 3.
3. Jackson, W. P. Synlett 1990, 536.
4. a) Suzuki, M.; Takada, H.; Noyori, R. J. Org. Chem. 1982, 47, 902.
5. b) Matsubara, S.; Takai, K.; Nozaki, H. Bull. Chem. Soc. Jpn. 1983, 56, 2029.
6. Without the addition of any Lewis acid no reaction occurred.
7. One of these might be an attack of the aromatic ring, which is known for BTP and Lewis acids. Apatu, J. O.; Chapman, D. C.; Heaney, H. J. Chem. Soc. Chem. Commun. 1981, 1079.
8. a) Criegee, R.; Schnorrenberg, W.; Becke, J. Justus Liebigs Ann. Chem. 1949, 565, 7.
9. b) Story, P.R.; Lee, B.; Bishop, C. E.; Denson, D. D.; Busch, P. J. Org. Chem. 1970, 35, 3059.
10. c) Jefford, C. W.; Boukouvalas, A. J. J. Synthesis 1988, 391.
11. Dry molecular sieves 4A was used and added to the reaction vessel prior to any other compound.
12. 9 (which might be formed by the reaction of tin(IV)-chloride with traces of water) and is thereby inhibiting a silicon-proton exchange reaction of the peroxide and HCl. We suppose that the addition of a hydroperoxide to the ketone is faster than the addition of the silylperoxide. This is in agreement with the observation of an overall reduced reaction rate upon addition of molecular sieves. The intermediate 3 (see below) can add to a second ketone to form ketone peroxides or rearrange to the Baeyer-Villiger product. Whilst the second addition is slowed down in the absence of HCl, the rearrangement is not affected, resulting in an overall increased lactone: ketone-peroxide ratio. For removal of HCl by molecular sieves, see: Terada, M.; Matsumoto, Y.; Nakamura, Y.; Mikami, K. Chem. Commun. 1997, 281. (Matrix Presented) Figure 3
13. 2): 2-propanol (2.5 h); 56% yield, p-toluenesulfonamide (13 h); 83%, (±)-trans-1,2-bis(tosylamido)-cyclohexane (18 h); 61%, pyridine (2 h); 83%, 2-aminopyridine (13 h); 59%, 2-(2-aminoethyl)pyridine (13 h); 81%, (±)-1-phenyl-ethylamine (27 h); 71%, 3-aminopropanol (18 h); 66%, ethylenediamine (4 h); 48%, 1,3-diaminopropane (2 h); 32%, 1,2-diaminobenzene (13 h); 72%.
14. This was checked by adding cyclohexene instead of ketone 1 to the oxidation system. In the case of alcohols and sulfonamides as ligands chlorohydrins were formed, whilst in the case of amine ligands no reaction occurred.
15. An octahedral complex is proposed, a geometry very common for tin(IV)-complexes. Nevertheless, some examples of 7- and 8-coordination exist for tin(IV) too. See: Harrisin, P. G. Chemistry of Tin; Blackie: Glasgow, 1989.
16. A standard procedure is the following: (Only dry solvents were used, the flask was heat-vacuum dried prior to use and the reaction was carried out under argon). To a mixture consisting of molecular sieves (4A, approx. 0.2 g) and 0.25 ml of a 1.0 molar solution of trans-1,2-(diamino)cyclohexane (in THF) in 7 ml dichloromethane tin(IV)-chloride was added (0.25 ml of a 1.0 molar solution in dichloromethane). The resulting suspension was cooled with an ice-bath and 2.0 ml of bis(trimethylsilyl) peroxide (1.0 molar solution in dichloromethane) was added. The mixture was stirred for 5-10 minutes and then the ketone (1.0 mmol) was added. The ice-bath was removed and the reaction was stirred at room temperature until all ketone was consumed (TLC-control). Solid sodium sulfite was added (0.3 g) and the suspension stirred for 3 h at room temperature. Then the mixture was filtered over 2 cm of silica and washed with 30 ml of ethyl acetate. The solvent was evaporated and the crude product was purified by flash-chromatography.
17. The proton- and carbon-NMR spectra were identical with published data.
18. 3, 67.5 MHz): 160.6; 136.6; 130.6; 128.0; 126.6; 83.3; 46.8; 26.1. The compound could not be obtained in an analytical pure form and was identified by conversion to the free alcohol via LAH-reduction.
19. For previous examples of enantioselective Baeyer-Villiger oxidations see: a) Bolm, C.; Schlingloff, G.; Weickhardt, K. Angew. Chem. Int. Ed. Engl. 1994, 33, 1848. b) Gusso, A.; Baccin, C.; Pinna, F.; Strukul, G.; Organometallics 1994, 13, 3442. c) Lopp, M.; Paju, A.; Kanger, T.; Pehk, T. Tetrahedron Lett. 1996, 37, 7583.
20. For previous examples of enantioselective Baeyer-Villiger oxidations see: a) Bolm, C.; Schlingloff, G.; Weickhardt, K. Angew. Chem. Int. Ed. Engl. 1994, 33, 1848. b) Gusso, A.; Baccin, C.; Pinna, F.; Strukul, G.; Organometallics 1994, 13, 3442. c) Lopp, M.; Paju, A.; Kanger, T.; Pehk, T. Tetrahedron Lett. 1996, 37, 7583.
21. For previous examples of enantioselective Baeyer-Villiger oxidations see: a) Bolm, C.; Schlingloff, G.; Weickhardt, K. Angew. Chem. Int. Ed. Engl. 1994, 33, 1848. b) Gusso, A.; Baccin, C.; Pinna, F.; Strukul, G.; Organometallics 1994, 13, 3442. c) Lopp, M.; Paju, A.; Kanger, T.; Pehk, T. Tetrahedron Lett. 1996, 37, 7583.