Ligands for asymmetric reactions

Organic compounds -- part of the class 532-570 series – Organic compounds – Heterocyclic carbon compounds containing a hetero ring...

Reexamination Certificate

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C549S006000, C549S216000, C568S454000

Reexamination Certificate

active

07094907

ABSTRACT:
The invention relates to a process for the manufacture of bidentate ligands of the formula IA and IIA, characterized in that N,N-(optionally substituted)dialkylamino phosphines bound to an aromatic carbon are lithiated in ortho-position and the lithiated compounds are further converted to said bidentate ligands:wherein X1is NR, O or S; X2is CHR1or CR1; X3is CHR2or NR2, or, if X2is CR1, X3is CR2or N; and R, R1and R2are radicals such as alkyl groups or R1and R2together form an annealed ring; Y1*, Y2* and Y1′* are, independently of each other, an element of the fifth group of the periodic table of elements as such or in thioxo or oxo form; Z1*, Z2*, Z3*, Z4*, Z1′*, Z2′* are, independently of each other, for example halogen, hydrogen, or an unsubstituted or substituted moiety selected from radicals such as alkyl groups; the substituents have otherwise the meanings given in the specification; and the ligands are capable of forming metal complexes, which can be used as catalysts in stereoselective synthesis, especially hydrogenation of various organic molecules.

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Tolmachev, A.A., “3-Phosphorylated N-Alkylindoles,” May 15, 1996, Heteroatom Chemistry, vol. 7, No. 6, pp. 525-531.
Kyba, E.P., “A Facile Synthesis of 1,2-Bis(phosphino)benzene and Related Alkylated Species,” Jul. 26, 1983, Organometallics, vol. 2, pp. 1877-1879.
K. Drewelies et al., “o- and m- Phenylene-bis(dichlorophosphane)-versatile, useful synthetic building blocks”, Angewandte Chemie. International Edition., vol. 21, No. 8, pp. 638-639, 1982, XP002192246, Verlag Chemie. Weinheim., DE ISSN: 0570-0833.
E. Kyba et al., “A novel synthesis of 1,2-diphosphorylbenzenes”, Tetrahedron Letters, vol. 22, No. 20, pp. 1875-1878, 1981, XP002192247 Elsevier Science Publishers, Amsterdam, NL ISSN: 0040-4039.
E. Kyba et al., “A facile synthesis of 1,2-bis(phosphino)benzene and related alkylated species”, Organometallics, vol. 2, No. 12, pp. 1877-1879, 1983, XP001063989, ACS, Columbus, OH, US ISSN: 0276-7333.
A.A. Tolmachev et al., “3-phosphorylated N-alkylindoles”, Heteroatom Chemistry, vol. 7, No. 6, pp. 525-531, 1996, XP008016372, VCH Publishers, Derfield Beach, FL, US ISSN: 1042-7163.

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