A new bifunctional asymmetric catalysis: An efficient catalytic asymmetric cyanosilylation of aldehydes [23]

Journal of the American Chemical Society

Volumn 121, Issue 11, 1999, Pages 2641-2642

  Hamashima, Yoshitaka ^a   Sawada, Daisuke ^a   Kanai, Motomu ^a   Shibasaki, Masakatsu ^a  

^a UNIVERSITY OF TOKYO   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

ALDEHYDE; ALUMINUM; CARBONYL DERIVATIVE;

CATALYSIS; CATALYST; CHEMICAL REACTION; CHEMICAL STRUCTURE; CHIRALITY; ENANTIOMER; GEOMETRY; HIGH PERFORMANCE LIQUID CHROMATOGRAPHY; LETTER; MOLECULAR MODEL;

EID: 0033599540     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja983895c     Document Type: Letter

References (23)

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2. (b) Catalytic Asymmetric Synthesis; Ojima, I., Ed.; VCH: New York, 1993.
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10. 3P(O), the yield was 12% under the same conditions. At -40 °C for 40 h, however, the reaction did not proceed at all.
11. 2). However, the naphthol moieties of this ligand were partly silylated during the reaction, whereas catalyst 1 was stable against silylation under the reaction conditions.
12. (a) Hwang, C.-D.; Hwang, D.-R.; Uang, B.-J. J. Org. Chem. 1998, 63, 6762-6763.
13. (b) Bolm, C.; Müller, P.; Harms, K. Acta Chem. Scand. 1996, 50, 305-315.
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17. The products of the opposite configuration were generally obtained by 3 (9 mol %) (-40 °C, 37 h): 5g gave R-6g (50% yield and 12% ee); 5a gave R-6a (56% yield and 10% ee); 5c gave R-6c (36% yield and 4% ee) with 3.
18. (a) Ooi, T.; Kagoshima, N.; Maruoka, K. J. Am. Chem. Soc. 1997, 119, 5754-5755.
19. (b) Murakata, M.; Jono, T.; Mizuno, Y.; Hoshino, O. J. Am. Chem. Soc. 1997, 119, 11713-11714.
20. Addition of ether, dimethyl sulfoxide, Hünig base, or acetonitrile gave lower ee values. Since the reaction pathway involving activation by the external phosphine oxide is negligible at -40 °C (ref 5), only an internal phosphine oxide can function as an activator of TMSCN, because the phosphine oxide exists at the appropriate position close to TMSCN in the reactive complex.
21. 3P(O)), as expected from the lower Lewis acidity.
22. 2 (0.35 mL). The resulting mixture was stirred for l h at room temperature and cooled to -40 °C. After the addition of an aldehyde (0.192 mmol), TMSCN (46 μL, 0.346 mmol) was slowly added over 10 h. After the time shown in Table 1, 2 N HCl (1.0 mL) was added to hydrolyze the product. The crude cyanohydrin was purified by flash chromatography on silica gel.
23. 3P(O) (40 mol %) (-40 °C for 36 h), whereas 1 gave 5-6g in 60% yield and in 56% ee under the same conditions.