Dimethylthiocarbamate (DMTC): An Alcohol Protecting Group

Organic Letters

Volumn 5, Issue 25, 2003, Pages 4755-4757

  Barma, D K ^a   Bandyopadhyay, A ^a   Capdevila, Jorge H ^b   Falck, J R ^a  

^a UNIVERSITY OF TEXAS SOUTHWESTERN MEDICAL CENTER   (United States)

^b VANDERBILT UNIVERSITY SCHOOL OF MEDICINE   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALCOHOL; CHEMICAL AGENT; CHLORIDE; CHROMIUM CHLORIDE; DIMETHYLTHIOCARBAMOYL CHLORIDE; FLUORINE DERIVATIVE; FUNCTIONAL GROUP; HYDROCHLORIC ACID; HYDROGEN PEROXIDE; LEWIS ACID; METAL; ORGANOLITHIUM COMPOUND; REAGENT; SODIUM DERIVATIVE; SODIUM HYDROXIDE; THIOCARBAMIC ACID; UNCLASSIFIED DRUG;

ARTICLE; HEAT; HYDROBORATION; METHODOLOGY; SYNTHESIS;

ALCOHOLS; MOLECULAR STRUCTURE; THIOCARBAMATES;

EID: 0347228972     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol0354573     Document Type: Article

References (22)

1. Greene, T. W.; Wuts, P. G. M. Protective Groups in Organic Synthesis, 3rd ed.; John Wiley and Sons: New York, 1999.
2. Recent examples: (a) Almog, J.; Zehavy, Y.; Cohen, S. Tetrahedron Lett. 2003, 44, 3285-3288. (b) Kessler, M.; Glatthar, R.; Giese, B.; Bochet, C. G. Org. Lett. 2003, 5, 1179-1181. (c) Ellervik, U. Tetrahedron Lett. 2003, 44, 2279-2281. (d) Miura, T.; Inazu, T. Tetrahedron Lett. 2003, 44, 1819-1821. (e) Dinkel, C.; Wichmann, O.; Schultz, C. Tetrahedron Lett. 2003, 44, 1153-1155. (f) Csavas, M.; Borbas, A.; Janossy, L.; Liptak, A. Tetrahedron Lett. 2003, 44, 631-635.
3. Recent examples: (a) Almog, J.; Zehavy, Y.; Cohen, S. Tetrahedron Lett. 2003, 44, 3285-3288. (b) Kessler, M.; Glatthar, R.; Giese, B.; Bochet, C. G. Org. Lett. 2003, 5, 1179-1181. (c) Ellervik, U. Tetrahedron Lett. 2003, 44, 2279-2281. (d) Miura, T.; Inazu, T. Tetrahedron Lett. 2003, 44, 1819-1821. (e) Dinkel, C.; Wichmann, O.; Schultz, C. Tetrahedron Lett. 2003, 44, 1153-1155. (f) Csavas, M.; Borbas, A.; Janossy, L.; Liptak, A. Tetrahedron Lett. 2003, 44, 631-635.
4. Recent examples: (a) Almog, J.; Zehavy, Y.; Cohen, S. Tetrahedron Lett. 2003, 44, 3285-3288. (b) Kessler, M.; Glatthar, R.; Giese, B.; Bochet, C. G. Org. Lett. 2003, 5, 1179-1181. (c) Ellervik, U. Tetrahedron Lett. 2003, 44, 2279-2281. (d) Miura, T.; Inazu, T. Tetrahedron Lett. 2003, 44, 1819-1821. (e) Dinkel, C.; Wichmann, O.; Schultz, C. Tetrahedron Lett. 2003, 44, 1153-1155. (f) Csavas, M.; Borbas, A.; Janossy, L.; Liptak, A. Tetrahedron Lett. 2003, 44, 631-635.
5. Recent examples: (a) Almog, J.; Zehavy, Y.; Cohen, S. Tetrahedron Lett. 2003, 44, 3285-3288. (b) Kessler, M.; Glatthar, R.; Giese, B.; Bochet, C. G. Org. Lett. 2003, 5, 1179-1181. (c) Ellervik, U. Tetrahedron Lett. 2003, 44, 2279-2281. (d) Miura, T.; Inazu, T. Tetrahedron Lett. 2003, 44, 1819-1821. (e) Dinkel, C.; Wichmann, O.; Schultz, C. Tetrahedron Lett. 2003, 44, 1153-1155. (f) Csavas, M.; Borbas, A.; Janossy, L.; Liptak, A. Tetrahedron Lett. 2003, 44, 631-635.
6. Recent examples: (a) Almog, J.; Zehavy, Y.; Cohen, S. Tetrahedron Lett. 2003, 44, 3285-3288. (b) Kessler, M.; Glatthar, R.; Giese, B.; Bochet, C. G. Org. Lett. 2003, 5, 1179-1181. (c) Ellervik, U. Tetrahedron Lett. 2003, 44, 2279-2281. (d) Miura, T.; Inazu, T. Tetrahedron Lett. 2003, 44, 1819-1821. (e) Dinkel, C.; Wichmann, O.; Schultz, C. Tetrahedron Lett. 2003, 44, 1153-1155. (f) Csavas, M.; Borbas, A.; Janossy, L.; Liptak, A. Tetrahedron Lett. 2003, 44, 631-635.
7. Recent examples: (a) Almog, J.; Zehavy, Y.; Cohen, S. Tetrahedron Lett. 2003, 44, 3285-3288. (b) Kessler, M.; Glatthar, R.; Giese, B.; Bochet, C. G. Org. Lett. 2003, 5, 1179-1181. (c) Ellervik, U. Tetrahedron Lett. 2003, 44, 2279-2281. (d) Miura, T.; Inazu, T. Tetrahedron Lett. 2003, 44, 1819-1821. (e) Dinkel, C.; Wichmann, O.; Schultz, C. Tetrahedron Lett. 2003, 44, 1153-1155. (f) Csavas, M.; Borbas, A.; Janossy, L.; Liptak, A. Tetrahedron Lett. 2003, 44, 631-635.
8. For other studies of protecting groups from our laboratories, see: (a) Falck, J. R.; Barma, D. K.; Venkataraman, S. K.; Baati, R.; Mioskowski, C. Tetrahedron Lett. 2002, 43, 963-966. (b) Falck, J. R.; Barma, D. K.; Baati, R.; Mioskowski, C. Angew. Chem., Int. Ed. 2001, 40, 1281-1283. (c) Baati, R.; Valleix, A.; Mioskowski, C.; Barma, D. K.; Falck, J. R. Org. Lett. 2000, 2, 485-487. (d) Cho, H.-S.; Yu, J.; Falck, J. R. J. Am. Chem. Soc. 1994, 116, 8354-8355. (e) Bolitt, V.; Mioskowski, C.; Shin, D. S.; Falck, J. R. Tetrahedron Lett. 1988, 29, 4583-4586.
9. For other studies of protecting groups from our laboratories, see: (a) Falck, J. R.; Barma, D. K.; Venkataraman, S. K.; Baati, R.; Mioskowski, C. Tetrahedron Lett. 2002, 43, 963-966. (b) Falck, J. R.; Barma, D. K.; Baati, R.; Mioskowski, C. Angew. Chem., Int. Ed. 2001, 40, 1281-1283. (c) Baati, R.; Valleix, A.; Mioskowski, C.; Barma, D. K.; Falck, J. R. Org. Lett. 2000, 2, 485-487. (d) Cho, H.-S.; Yu, J.; Falck, J. R. J. Am. Chem. Soc. 1994, 116, 8354-8355. (e) Bolitt, V.; Mioskowski, C.; Shin, D. S.; Falck, J. R. Tetrahedron Lett. 1988, 29, 4583-4586.
10. For other studies of protecting groups from our laboratories, see: (a) Falck, J. R.; Barma, D. K.; Venkataraman, S. K.; Baati, R.; Mioskowski, C. Tetrahedron Lett. 2002, 43, 963-966. (b) Falck, J. R.; Barma, D. K.; Baati, R.; Mioskowski, C. Angew. Chem., Int. Ed. 2001, 40, 1281-1283. (c) Baati, R.; Valleix, A.; Mioskowski, C.; Barma, D. K.; Falck, J. R. Org. Lett. 2000, 2, 485-487. (d) Cho, H.-S.; Yu, J.; Falck, J. R. J. Am. Chem. Soc. 1994, 116, 8354-8355. (e) Bolitt, V.; Mioskowski, C.; Shin, D. S.; Falck, J. R. Tetrahedron Lett. 1988, 29, 4583-4586.
11. For other studies of protecting groups from our laboratories, see: (a) Falck, J. R.; Barma, D. K.; Venkataraman, S. K.; Baati, R.; Mioskowski, C. Tetrahedron Lett. 2002, 43, 963-966. (b) Falck, J. R.; Barma, D. K.; Baati, R.; Mioskowski, C. Angew. Chem., Int. Ed. 2001, 40, 1281-1283. (c) Baati, R.; Valleix, A.; Mioskowski, C.; Barma, D. K.; Falck, J. R. Org. Lett. 2000, 2, 485-487. (d) Cho, H.-S.; Yu, J.; Falck, J. R. J. Am. Chem. Soc. 1994, 116, 8354-8355. (e) Bolitt, V.; Mioskowski, C.; Shin, D. S.; Falck, J. R. Tetrahedron Lett. 1988, 29, 4583-4586.
12. For other studies of protecting groups from our laboratories, see: (a) Falck, J. R.; Barma, D. K.; Venkataraman, S. K.; Baati, R.; Mioskowski, C. Tetrahedron Lett. 2002, 43, 963-966. (b) Falck, J. R.; Barma, D. K.; Baati, R.; Mioskowski, C. Angew. Chem., Int. Ed. 2001, 40, 1281-1283. (c) Baati, R.; Valleix, A.; Mioskowski, C.; Barma, D. K.; Falck, J. R. Org. Lett. 2000, 2, 485-487. (d) Cho, H.-S.; Yu, J.; Falck, J. R. J. Am. Chem. Soc. 1994, 116, 8354-8355. (e) Bolitt, V.; Mioskowski, C.; Shin, D. S.; Falck, J. R. Tetrahedron Lett. 1988, 29, 4583-4586.
13. Review of thiocarbamate syntheses: Walter, W.; Bode, K. D. Angew. Chem., Int. Ed. Engl. 1967, 6, 281-293.
14. The ability of thionocarbamates to stabilize organocopper reagents has been exploited for the cross-coupling of α,β-dialkoxy-and α-alkoxy-β-aminostannanes: Mohapatra, S.; Bandyopadhyay, A.; Barma, D. K.; Capdevila, J. H.; Falck, J. R. Org. Lett. 2003, 5, 4759-4762.
15. Commercial N,N-dimethylthiocarbamoyl chloride can vary in quality. Impure samples were refined by molecular (Kugelrohr) distillation, bp 65 °C at 0.2 mmHg, to give a white solid (mp 41°C) that could be stored indefinitely at room temperature under an argon atmosphere.
16. 2 (5 mL) containing DMAP (0.1 mmol) under an argon atmosphere. After 2-10 h, the reaction mixture was filtered through a small pad of silica gel, and the filter cake was washed with EtOAc (5 mL). The combined filtrate was concentrated under reduced pressure, and the residue was dissolved in a 2 M THF solution of dimethylamine (4 mL). After 2-4 h, all volatiles were removed in vacuo, and the residue was chromatographed over silica gel affording thiocarbamoylated alcohol.
17. 3, 75 MHz) δ 14.21, 22.74, 25.23, 29.28, 29.46, 29.60, 31.08, 31.92, 37.87, 38.06, 42.87, 72.19, 78.88, 187.82, 187.95.
18. The Neuman-Kwart rearrangement (O → S migration) normally becomes significant only at temperatures of ≥ 220°C, e.g.: Relles, H. M.; Pizzolato, G. J. Org. Chem. 1968, 33, 2249-2253.
19. (a) Barma, D. K.; Kundu, A.; Zhang, H.; Mioskowski, C.; Falck, J. R. J. Am. Chem. Soc. 2003, 125, 3218-3219.
20. (b) Barma, D. K.; Baati, R.; Valleix, A.; Mioskowski, C.; Falck, J. R. Org. Lett. 2001, 3, 4237-4238.
21. 4. Concentration under reduced pressure and purification of the residue over silica gel afforded pure alcohol (85-90%).
22. Walter, W.; Wohlers, K. Ann. Chem. 1971, 752, 115-135.