Improved preparation of tosyldiazomethane

Tetrahedron Letters

Volumn 41, Issue 29, 2000, Pages 5489-5493

  Plessis, C ^a   Uguen, D ^a   De Cian, A ^a   Fischer, J ^a  

^a CNRS   (France)

Author keywords

[No Author keywords available]

Indexed keywords

SULFONE DERIVATIVE; TOSYLDIAZOMETHANE; UNCLASSIFIED DRUG;

ARTICLE; CHEMICAL REACTION; CRYSTALLIZATION; DECOMPOSITION; NUCLEAR MAGNETIC RESONANCE IMAGING; SYNTHESIS; THIN LAYER CHROMATOGRAPHY; X RAY ANALYSIS;

EID: 0034662171     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(00)00763-2     Document Type: Article

References (13)

1. Brückner, R.; Peiseler, B. Tetrahedron Lett. 1988, 29, 5233-5236.
2. Van Leusen, A. M.; Strating, J. Org. Synth. 1977, 57, 95-102. This procedure is based on the work of Strating and van Leusen (van Leusen, A. M.; Strating, J. Rec. Trav. Chim. Pays-Bas 1965, 84, 151-164 and references cited therein), who discovered this class of diazo compounds.
3. 1H NMR spectra.
4. Sulfones 1 cannot be obtained from the corresponding p-tolyl alkylsulfones by using the diazo transfer method of Regitz (see: Dieckmann, J. J. Org. Chem. 1965, 30, 2272-2275). Recently, a procedure based on the related alumina-induced decomposition of 1-diazo-1-tosyl-acetophenone has been proposed (Korneev, S.; Richter, C. Synthesis 1995, 1248-1250). However, owing to the ease with which the starting carbamate 2a is prepared, this method presents no clear advantage over the van Leusen's process.
5. Sulfones 1 cannot be obtained from the corresponding p-tolyl alkylsulfones by using the diazo transfer method of Regitz (see: Dieckmann, J. J. Org. Chem. 1965, 30, 2272-2275). Recently, a procedure based on the related alumina-induced decomposition of 1-diazo-1-tosyl-acetophenone has been proposed (Korneev, S.; Richter, C. Synthesis 1995, 1248-1250). However, owing to the ease with which the starting carbamate 2a is prepared, this method presents no clear advantage over the van Leusen's process.
6. Lee, J. G.; Kwak, K. H.; Hwang, J. P. Tetrahedron Lett. 1990, 31, 6677-6680.
7. 13C NMR: 14.1, 21.8, 58.5, 65.4, 128.5, 130.6, 135.4, 145.9, 152.4. The 3-1 conversions were performed according to Ref. 2 except that the flask containing the basic alumina (Merck; 3 g/mmol) was first heated in an oven at 300°C for 12 h, then immediately transferred in a desiccator where it was allowed to cool to rt in vacuo. It was then connected to an argon line, and cooled (ice/methanol) before the ether was added. After 12 h stirring at rt, on a 7.2 g scale (25 mmol), the diazosulfone 1a was obtained as bright-yellow needles (3.3 g; 67.2%) after recrystallisation from a 2:1 ether:hexane mixture.
8. 3.
9. 2. Refinements against l Fl using the OpenMoleN package on a DEC Alpha workstation and anisotropic temperature factors for all non-hydrogen atoms. The absolute structure was determined refining Flack's x parameter. Final results: R(F)=0.052, Rw(F)=0.068, GOF=1.657.
10. (a) Regitz, M.; Waas, G. Diazo Compounds. Properties and Synthesis; Academic Press: London, 1986;
11. (b) To be compared with the 1.66 Å value obtained for the corresponding C-S bond in anionised benzyl phenylsulfone (Reetz, M. T.; Hütte, S.; Goddard, R. Eur. J. Org. Chem. 1999, 2475-2478 and references cited therein);
12. (c) Cerioni, G.; Culeddu, N.; Saba, A. Magn. Reson. Chem. 1993, 31, 829-831;
13. (d) Engberts, J. B. F. N.; Zwanenburg, B. Tetrahedron 1968, 24, 1737-1754.