Reduction of organic halides with tri-2-furanylgermane: Stoichiometric and catalytic reaction

Synlett

Volumn , Issue 9, 1999, Pages 1415-1416

  Nakamura, Tomoaki ^a   Yorimitsu, Hideki ^a   Shinokubo, Hiroshi ^a   Oshima, Koichiro ^a  

^a KYOTO UNIVERSITY   (Japan)

Author keywords

Radical reaction; Reduction; Tri 2 furanylgermane; Triethylborane

Indexed keywords

BORANE DERIVATIVE; BROMIDE; CHLORIDE; GERMANIUM DERIVATIVE; IODIDE; ORGANOHALOGEN DERIVATIVE; RADICAL;

ARTICLE; CATALYSIS; CHEMICAL STRUCTURE; CYCLIZATION; REACTION ANALYSIS; REDUCTION; STOICHIOMETRY;

EID: 0032872849     PISSN: 09365214     EISSN: None     Source Type: Journal    
DOI: 10.1055/s-1999-2874     Document Type: Article

References (18)

1. Comprehensive Organic Synthesis, Trost, B. M.; Fleming, I.; Eds., Pergamon Press: New York, 1991, Vol.8, Chap.4.
2. Davis, A. D. Organotin Chemistry, WILEY-VCH, Weinheim, 1997.
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6. a) Nozaki, K.; Oshima, K.; Utimoto, K. J. Am. Chem. Soc. 1987, 109, 2547.
7. b) Ichinose, Y.; Nozaki, K.; Wakamatsu, K.; Oshima, K.; Utimoto, K. Tetrahedron Lett. 1987, 28, 3709.
8. 4 has been reported. Corey, E. J.; Suggs, J. W. J. Org. Chem. 1975, 40, 2554.
9. 4/hydrocarbon system has been reported. Gevorgyan, V. N.; Ignatovich, L. M.; Lukevics, E. J. Organomet. Chem. 1985, 284, C31. However, no reaction using tri-2-furanylgermane has been reported.
10. 2O and extracted with EtOAc (50 mL × 3). The combined organic layer was dried and concentrated in vacuo to give a solid. Recrystallization from toluene provided tetra-2-furanylgermane (26 g, 77 mmol) in 85% yield. Lithium metal (0.83 g, 120 mmol) was added to a solution of tetra-2-furanylgermane (10.2 g, 30 mmol) in THF (30 mL) and the resulting mixture was stirred for 1.5 h at 25 °C. Extractive workup (EtOAc, brine) followed by silica-gel column purification gave tri-2-furanylgermane (1, 5.8 g, 21 mmol) in 70 % yield.
11. a) Ingold, K. U.; Lusztyk, J.; Scaiano, J. C. J. Am. Chem. Soc. 1984, 106, 343.
12. b) Beckwith, A. L. J.; Schiesser, C. H. Tetrahedron 1985, 41, 3925.
13. c) Pike, P.; Hershberger, S.; Hershberger, J. Tetrahedron 1988, 44, 6295.
14. Only one example can be found in the literature. Gupta, V.; Kahne, D. Tetrahedron Lett., 1993, 34, 591.
15. 4 (2.0 mmol) at 25 °C for 12 h in the presence of 1 (0.02 mmol) provided dodecane in 96% yield.
16. Catalytic reduction was examined in several solvents such as ethanol, hexane, tetrahydrofuran, and acetonitrile. Among them, THF gave the best result.
17. 3GeH gave better yield compared to tri-2-furanylgermane 1. For instance, the use of 1 in the reaction of 6b provided 7b in only 20% yield.
18. This work is supported by Grant-in-Aid for Scientific Research (No. 10875178) from the Ministry of Education , Science, Sports and Culture, Government of Japan.