Methods for formation of aryl-sulfur and aryl-selenium...

Organic compounds -- part of the class 532-570 series – Organic compounds – Sulfur containing

Reexamination Certificate

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C568S077000, C562S899000, C502S165000, C252S183130

Reexamination Certificate

active

07112697

ABSTRACT:
A mild, palladium-free synthetic protocol for the cross-coupling reaction of vinyl or aryl iodides and thiols or selenols using, in certain embodiments, 10 mol % CuI and 10 mol % neocuproine, with NaOt-Bu as the base, in toluene at 110 ° C. A variety of vinyl/aryl sulfides and vinyl/aryl selenides can be synthesized in excellent yields from readily available iodides and thiols or selenols.

REFERENCES:
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patent: 6762329 (2004-07-01), Marcoux et al.
patent: 2003/0088128 (2003-05-01), Marcoux et al.
Alexey V. Kalinin, Justin F. Bower, Peter Riebel, and Victor Snieckus, “The Directed Ortrho Metalation—Ullmann Connection. A New Cu(I)-Catalyzed Variant for the Synthesis of Substituted Diaryl Ethers,”J. Org. Chem., 1999 American Chemical Society, p. 2986-87, vol. 64, published on Web Apr. 15, 1999.
Claudio Palomo, Mikel Oiarbide, Rosa López, and Enrique Gómez-Bengoa, “Phosphazene bases for the preparation of biaryl thioathers from aryl iodides and arenthoils,”Tetrahedron Letters, 2000 Elseview Science, Ltd., p. 1283-86, vol. 41.
Rattan K. Gujadhur, Craig G. Bates, and D. Venkataraman, “Formation of Aryl-Nitrogen, Aryl-Oxygen, and Aryl-Carbon Bonds Using Well-Defined Copper(I)-Based Catalysts,”Organic Letters, 2001 American Chemical Society, p. 4315-17, vol. 3, No. 26, published on Web Nov. 22, 2001.
Craig G. Bates, Rattan K. Gujadhur, and D. Venkataraman, “A General Method for the Formation of Aryl-Sulfur Bonds Using Copper(I) Catalysts,”Organic Letters, 2002 American Chemical Society, p. 2803-08, vol. 4, No. 16, published on Web Jul. 12, 2002.
Fuk Yee Kwong and Stephen L. Buchwald, “A General, Efficient, and Inexpensive Catalyst System for the Coupling of Aryl Iodides and Thiols,”Organic Letters, 2002 American Chemical Society, p. 3517-20, vol. 4, No. 20, published on Web Sep. 11, 2002.
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