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Volumn 73, Issue 3, 2008, Pages 813-819

Tetranuclear BINOL-titanium complex in selective direct aldol additions

Author keywords

[No Author keywords available]

Indexed keywords

COMPLEXATION; KETONES; REACTION KINETICS; REGIOSELECTIVITY; TITANIUM COMPOUNDS;

EID: 38849148420     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo7014054     Document Type: Article
Times cited : (26)

References (85)
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    • For an overview see the following. (a) Acid catalysis: Yamamoto, H.; Futatsugi, K. Angew. Chem. 2005, 117, 1958.
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    • (c) Titanium complexes: Mikami, K.; Matsumoto, Y.; Shiono, T. In Science of Synthesis; Bellus, D., Jacobsen, N. E., Ley, S. V., Noyori, R., Regitz, M., Reider, P. J., Schaumann, E., Shinkai, I., Thomas, E. J., Trost, B. M., Eds.: Thieme: Stuttgart, 2003; Product class 10: Organometallic Complexes of Titanium.
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    • Applications to organic synthesis: Titanium and Zirconium in Organic Synthesis; Marek, I., Ed.: Wiley-VCH: Weinheim 2002.
    • (d) Applications to organic synthesis: Titanium and Zirconium in Organic Synthesis; Marek, I., Ed.: Wiley-VCH: Weinheim 2002.
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    • Heathcock, C. H., Chapter 1.6; Kim, B. M., Williams, S. F., Masamune, S., Chapter 1.7; Rathke, M. W., Weipert, P., Chapter 1.8; Paterson, I., Chapter 1.9; Gennari, C., Chapter 2.4 In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Heathcock, C. H., Eds.: Pergamon: Oxford, 1993, 2.
    • (a) Heathcock, C. H., Chapter 1.6; Kim, B. M., Williams, S. F., Masamune, S., Chapter 1.7; Rathke, M. W., Weipert, P., Chapter 1.8; Paterson, I., Chapter 1.9; Gennari, C., Chapter 2.4 In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Heathcock, C. H., Eds.: Pergamon: Oxford, 1993, Vol. 2.
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    • The experimental procedure was the same as that given by Mikami et al. The catalyst was obtained as dark red rectangular crystals. A single crystal structure analysis was made of a suitable crystal. The complex was found to crystallize in the cubic space group F43c. a = b = c = 32.348 Å; R1 = 0.049, wR2 = 0.118. Crystallographic data have been deposited at the Cambridge Crystal Data Centre (CCDC 279234). This material can be obtained upon request to CCDC, 12 Union Road, Cambridge 1EZ, U.K. (http://www.ccdc.cam.ac.uk; email: deposit@ccdc.cam.ac.uk). The structure was refined with SHELX97 (Sheldrick, G.M. SHELX97. Program for the Refinement of Crystal Structures; Universität Göttingen: Göttingen, 1997.)
    • The experimental procedure was the same as that given by Mikami et al. The catalyst was obtained as dark red rectangular crystals. A single crystal structure analysis was made of a suitable crystal. The complex was found to crystallize in the cubic space group F43c. a = b = c = 32.348 Å; R1 = 0.049, wR2 = 0.118. Crystallographic data have been deposited at the Cambridge Crystal Data Centre (CCDC 279234). This material can be obtained upon request to CCDC, 12 Union Road, Cambridge 1EZ, U.K. (http://www.ccdc.cam.ac.uk; email: deposit@ccdc.cam.ac.uk). The structure was refined with SHELX97 (Sheldrick, G.M. SHELX97. Program for the Refinement of Crystal Structures; Universität Göttingen: Göttingen, 1997.)
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    • So far, the catalysts loadings for similar reactions range usually between 2 and 20 mol %; recently, Ding et al. presented an enantioselective carbonyl-ene reaction with comparable low catalyst loadings: Yuan, Y.; Zhang, X.; Ding, K. Angew. Chem. Int. Ed. 2003, 42, 5478.
    • So far, the catalysts loadings for similar reactions range usually between 2 and 20 mol %; recently, Ding et al. presented an enantioselective carbonyl-ene reaction with comparable low catalyst loadings: Yuan, Y.; Zhang, X.; Ding, K. Angew. Chem. Int. Ed. 2003, 42, 5478.
  • 51
    • 38849189802 scopus 로고    scopus 로고
    • Typical Experimental Procedure. One equivqlent of aldehyde and 1.5 equiv of ketone were mixed at room temperature. If problems with the solubility occured, small amounts of CH2Cl2 were used as solvent, then 0.2 mol, of the catalyst was added. The progress of the reaction was monitored by TLC, and when the turnover was complete, the reaction mixture was diluted with diethyl ether and the reaction was quenched with aqueous NH 4Cl. The organic layer was separated, dried (MgSO4, and filtered, and the ether was removed in vacuo. Column chromatography (hexane/ethyl acetate) afforded the pure aldols. Yields have not been optimized. Large amounts of recovered aldehyde indicate the necessity to use longer reacion times or higher reaction temperatures in some cases
    • 4), and filtered, and the ether was removed in vacuo. Column chromatography (hexane/ethyl acetate) afforded the pure aldols. Yields have not been optimized. Large amounts of recovered aldehyde indicate the necessity to use longer reacion times or higher reaction temperatures in some cases.
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    • See Supporting Information
    • See Supporting Information.
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    • 1. a = 12.024 Å, b = 10.6931 Å, c = 7.1249 Å; R1 = 0.025, wR2 = 0.061. Crystallographic data have been deposited at the Cambridge Crystal Data Centre (CCDC 279235). This material can be obtained upon request to CCDC, 12 Union Road, Cambridge 1EZ, U.K. (http://www.ccdc.cam.ac.uk; email: deposit@ccdc.cam.ac.uk).
    • 1. a = 12.024 Å, b = 10.6931 Å, c = 7.1249 Å; R1 = 0.025, wR2 = 0.061. Crystallographic data have been deposited at the Cambridge Crystal Data Centre (CCDC 279235). This material can be obtained upon request to CCDC, 12 Union Road, Cambridge 1EZ, U.K. (http://www.ccdc.cam.ac.uk; email: deposit@ccdc.cam.ac.uk).
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    • Stereochemical investigation of the ketalacetal 19d and determination of the relative stereochemistry. NOE effects are visualized with green arrows. See Supporting Informations. (Chemical Equation Presented)
    • Stereochemical investigation of the ketalacetal 19d and determination of the relative stereochemistry. NOE effects are visualized with green arrows. See Supporting Informations. (Chemical Equation Presented)
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    • Calculated structure of the protected aldol 22 (geometric optimization/SymApps). NOE effects are visualized with green arrows. See Supporting Information. (Chemical Equation Presented)
    • Calculated structure of the protected aldol 22 (geometric optimization/SymApps). NOE effects are visualized with green arrows. See Supporting Information. (Chemical Equation Presented)
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    • Organoaluminium-promoted direct aldol condensations: (a) Tsuji, J.; Yamada, T.; Kaito, M.; Mandai, T. Tetrahedron Lett. 1979, 24, 2257.
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    • Similar results of kinetically controlled regioselectivities in organocatalyzed direct aldol additions depending on the bulkiness of unsymmetrical ketones used were reported by Kano, T, Tokuda, O, Takai, J, Maruoka, K. Chem. Asian J. 2006, 1, 210
    • Similar results of kinetically controlled regioselectivities in organocatalyzed direct aldol additions depending on the bulkiness of unsymmetrical ketones used were reported by Kano, T.; Tokuda, O.; Takai, J.; Maruoka, K. Chem. Asian J. 2006, 1, 210.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.