Lithium Hydroxide → 2'-Diphenylphosphinyl-2-hydroxy-1,1'-binaphthyl

HRID 1067874

Reaktionsgleichung

Reaktionsgleichung von HRID 1067874
C1(C2C3C(=CC=CC=3)C=CC=2)C(O)=CC=C2C=1C=CC=C2.FC(F)(F)S(OS(C(F)(F)F)(=O)=O)(=O)=O.FC(F)(F)S(OC1C=CC2C(=CC=CC=2)C=1C1C2C(=CC=CC=2)C=CC=1OS(C(F)(F)F)(=O)=O)(=O)=O.C1(P(=O)C2C=CC=CC=2)C=CC=CC=1.[C:87]1([P:93]([C:123]2[CH:128]=[CH:127][CH:126]=[CH:125][CH:124]=2)([C:95]2[CH:104]=[CH:103][C:102]3[C:97](=[CH:98][CH:99]=[CH:100][CH:101]=3)[C:96]=2[C:105]2[C:114]3[C:109](=[CH:110][CH:111]=[CH:112][CH:113]=3)[CH:108]=[CH:107][C:106]=2[O:115]S(C(F)(F)F)(=O)=O)=[O:94])[CH:92]=[CH:91][CH:90]=[CH:89][CH:88]=1.[OH-].[Li+]>C(Cl)Cl.N1C=CC=CC=1>[C:123]1([P:93]([C:87]2[CH:88]=[CH:89][CH:90]=[CH:91][CH:92]=2)([C:95]2[CH:104]=[CH:103][C:102]3[C:97](=[CH:98][CH:99]=[CH:100][CH:101]=3)[C:96]=2[C:105]2[C:114]3[C:109](=[CH:110][CH:111]=[CH:112][CH:113]=3)[CH:108]=[CH:107][C:106]=2[OH:115])=[O:94])[CH:124]=[CH:125][CH:126]=[CH:127][CH:128]=1

Komponenten

9

Edukt 6

HCID 3939Lithium HydroxideHCID 67749Trifluoromethanesulfonic anhydrideHCID 254003Diphenylphosphine oxideHCID 389883(S)-(+)-1,1'-Bi-2-naphthol bis(trifluoromethanesulfonate)HCID 27552601-(1-Naphthyl)-2-naphthol3×HCID 104385762'-Diphenylphosphinyl-2-trifluoromethanesulfonyloxy-1,1'-binaphthyl2×

Produkt 1

HCID 44179852'-Diphenylphosphinyl-2-hydroxy-1,1'-binaphthyl

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 1049PyridineLösungsmittelHCID 6344DichloromethaneLösungsmittel

Versuchsvorschrift

An optically active binaphthol (VII) as a starting material is reacted by a method described in the literature (M. Vondenhof and J. Mattay, Tetrahedron Lett., 1990, Vol. 31, pp . 985-988; L. Kurz, G. Lee, D. Morgans, Jr., M. J. Waldyke, and T. Ward, Tetrahedron Lett., 1990, Vol. 31, pp. 6321-6324) and by a method described in the literature (Y. Uozumi, A. Tanahashi, S. -Y. Lee, and T. Hayashi, J. Org. Chem., 1993, Vol. 58, pp. 1945-1948). That is, the binaphthol (VII) is reacted with trifluoromethanesulfonic anhydride (Tf2O) using pyridine in methylene chloride to convert compound (VII) to 2,2′-bis(trifluoromethanesulfonyl-oxy)-1,1′-binaphthyl (VIII), which is reacted with diphenylphosphine oxide (Ph2PHO) in the presence of a catalytic amount of a palladium-phosphine complex, whereby 2′-diphenylphosphinyl-2-trifluoromethanesulfonyloxy-1,1′-binaphthyl (IX) can be synthesized. Compound (IX) is hydrolyzed with lithium hydroxide (LiOH) to obtain 2′-diphenylphosphinyl-2-hydroxy-1,1′-binaphthyl (XVIII), which is brominated in dioxane to obtain 2′-diphenylphosphinyl-2-hydroxy-6-bromo-1,1′-binaphthyl (XIX). Compound (XIX) is reduced with trichlorosilane (HSiCl3) to obtain 2′-diphenylphosphino-2-hydroxy-6-bromo-1,1′-binaphthyl (XX), which is reacted with 2-vinyl-5,5-dimethyl-1,3-dioxa-2-borinane using a palladium catalyst by a method described in the literature (Y. Miyaura and A. Suzuki, J. C. S. Chem. Commun., 1979, p. 866) to obtain 2′-diphenylphosphino-2-hydroxy-6-vinyl-1,1′-binaphthyl (XXI).

Aufarbeitung

  1. customcan be synthesized

Quellen und Nachweise

ORD-Eintrag
ord-9275fa70e77f40ac89d77ce3cbfb2c1f
Quelldatensatz
uspto-grants-2001_06
Patentnummer
US06248848B1

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