Highly efficient synthesis of optically pure 5,5′,6,6′,7, 7′,8,8′-octahydro-1,1′-bi-2-naphthol and -naphthylamine derivatives by partial hydrogenation of 1,1′-binaphthyls with carbon nanofiber supported ruthenium nanoparticles
2,2′-Dimethoxy- and 2,2′-di(methoxymethy)oxy-1,1′- binaphthyl are well known as precursors for the 3,3′-disubstituted BINOL derivatives. (a) Cram, D. J.; Helgeson, R. C.; Peacock, S. C.; Kaplan, L. J.; Domeier, L. A.; Moreau, P.; Koga, K.; Mayer, J. M.; Chao, Y.; Siegel, M. G.; Hoffman, D. H. G.; Sogah, D. Y. J. Org. Chem. 1978, 43, 1930.
2,2′-Dimethoxy- and 2,2′-di(methoxymethy)oxy-1,1′- binaphthyl are well known as precursors for the 3,3′-disubstituted BINOL derivatives. (a) Cram, D. J.; Helgeson, R. C.; Peacock, S. C.; Kaplan, L. J.; Domeier, L. A.; Moreau, P.; Koga, K.; Mayer, J. M.; Chao, Y.; Siegel, M. G.; Hoffman, D. H. G.; Sogah, D. Y. J. Org. Chem. 1978, 43, 1930.
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(b) Lingenfelter, D. S.; Helgeson, R. C.; Cram, D. J. J. Org. Chem. 1981, 46, 393.
Both BINOL and H8-BINOL lose their optical rotations by heating in alcohols over 100°C (∼2, and such partial racemization accelerates under acidic or basic conditions ∼56, Encyclopedia of Reagents for Organic Synthesis; Paquette, L. A, Ed, John Wiley & Sons: New York, 1995; 1, p 397. Also see ref 2a
8-BINOL lose their optical rotations by heating in alcohols over 100°C (∼2%), and such partial racemization accelerates under acidic or basic conditions (∼56%). Encyclopedia of Reagents for Organic Synthesis; Paquette, L. A., Ed.; John Wiley & Sons: New York, 1995; Vol. 1, p 397. Also see ref 2a.
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The Pd/C-catalyzed reaction of (R)-BINOL can be performed at S/C, 100, but severe reaction conditions (100°C, 80 atm) are required to obtain H8-BINOL (99.7% ee) in high yields; see ref 7d
8-BINOL (99.7% ee) in high yields; see ref 7d.
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Optically pure H8-BINAP is generally obtained by optical resolution of racemic H8-bis(diphenylphosphinyl)-1,1′- binaphthyl (H8-BINAPO, which is prepared from (±)-BINOL, followed by reduction with trichlorosilane; see ref 7a
8-BINAPO), which is prepared from (±)-BINOL, followed by reduction with trichlorosilane; see ref 7a.
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Motoyama, Y.; Takasaki, M.; Higashi, K.; Yoon, S.-H.; Mochida, I.; Nagashima, H. Chem. Lett. 2006, 35, 876.
The CNFs are classified into three types: graphite layers are perpendicular (platelet: CNF-P), parallel (tubular: CNF-T), and stacked obliquely (herringbone: CNF-H). These three CNFs can be synthesized selectively in large scales; see: (a) Rodriguez, N. M. J. Mater. Res. 1993, 8, 3233.
The CNFs are classified into three types: graphite layers are perpendicular (platelet: CNF-P), parallel (tubular: CNF-T), and stacked obliquely (herringbone: CNF-H). These three CNFs can be synthesized selectively in large scales; see: (a) Rodriguez, N. M. J. Mater. Res. 1993, 8, 3233.
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and
(b) Tanaka, A.; Yoon, S.-H.; Mochida, I. Carbon 2004, 42, 591 and 1291.
The solvent strongly affected the reaction rate; the hydrogenations of BINOL in THF and dichloroethane were both sluggish, and the H8-BINOL was obtained in <10% yields along with the formation of H4-BINOL in ca. 20 and 50% yields, respectively
4-BINOL in ca. 20 and 50% yields, respectively.
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In the Pd/C-catalyzed reactions, similar results and explanations were reported; see ref 7d
In the Pd/C-catalyzed reactions, similar results and explanations were reported; see ref 7d.
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DABN 1f is easily soluble in THF, but the hydrogenation of 1f with Ru/CNF-P in THF at 100°C did not proceed.
DABN 1f is easily soluble in THF, but the hydrogenation of 1f with Ru/CNF-P in THF at 100°C did not proceed.
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Murdoch reported that chiral BINAP could be synthesized from optically pure DABN. Brown, K. J.; Berry, M. S.; Waterman, K. C.; Lingenfelter, D.; Murdoch, J. R. J. Am. Chem. Soc. 1984, 106, 4717.
Murdoch reported that chiral BINAP could be synthesized from optically pure DABN. Brown, K. J.; Berry, M. S.; Waterman, K. C.; Lingenfelter, D.; Murdoch, J. R. J. Am. Chem. Soc. 1984, 106, 4717.
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HPLC analysis was performed on an UV/vis detector (254 nm) using Daicel CHIRALCEL OD-H (flow rate = 0.5 mL/min).
HPLC analysis was performed on an UV/vis detector (254 nm) using Daicel CHIRALCEL OD-H (flow rate = 0.5 mL/min).
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