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Volumn 72, Issue 26, 2007, Pages 10264-10267

Diastereoselective production of homoallylic alcohols bearing quaternary centers from γ-substituted allylic indiums and ketones

Author keywords

[No Author keywords available]

Indexed keywords

ALLYLIC HALIDES; ALLYLIC INDIUMS; DIASTEREOSELECTIVE PRODUCTION; QUATERNARY CENTERS;

EID: 37549061084     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo701899j     Document Type: Article
Times cited : (29)

References (51)
  • 1
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    • Trost, B. M, Ed, Pergamon Press: Oxford, U.K
    • (a) Comprehensive Organic Syntheses; Trost, B. M., Ed.; Pergamon Press: Oxford, U.K., 1991; Vol. 2.
    • (1991) Comprehensive Organic Syntheses , vol.2
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    • Trost, B. M, Ed, Pergamon Press: Oxford, U.K
    • (b) Comprehensive Organic Syntheses; Trost, B. M., Ed.; Pergamon Press: Oxford, U.K., 1991; Vol. 1.
    • (1991) Comprehensive Organic Syntheses , vol.1
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    • Otera, J, Ed, Wiley-VCH: Weinheim, Germany, Chapter 10
    • (a) Chemler, S. R.; Roush, W. R. In Modern Carbonyl Chemistry; Otera, J., Ed.; Wiley-VCH: Weinheim, Germany, 2000; Chapter 10.
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    • Chemler, S.R.1    Roush, W.R.2
  • 8
    • 0037073196 scopus 로고    scopus 로고
    • For stereoselective additions to simple ketones, see: (a) Using tin-based reagents see: Yasuda, M.; Hirata, K.; Nishino, M.; Yamamoto, A.; Baba, A. J. Am. Chem. Soc. 2002, 124, 13442 and see references cited therein,
    • For stereoselective additions to simple ketones, see: (a) Using tin-based reagents see: Yasuda, M.; Hirata, K.; Nishino, M.; Yamamoto, A.; Baba, A. J. Am. Chem. Soc. 2002, 124, 13442 and see references cited therein,
  • 9
    • 34247857460 scopus 로고    scopus 로고
    • For a zinc version (allylic zincs were prepared from Zn (5 equiv), LiCl (1.2 equiv), and allyl halides (1 equiv)) see: Ren, H.; Dunet, G.; Mayer, P.; Knochel, P. J. Am. Chem. Soc. 2007, 129, 5376.
    • (b) For a zinc version (allylic zincs were prepared from Zn (5 equiv), LiCl (1.2 equiv), and allyl halides (1 equiv)) see: Ren, H.; Dunet, G.; Mayer, P.; Knochel, P. J. Am. Chem. Soc. 2007, 129, 5376.
  • 10
    • 0001441913 scopus 로고    scopus 로고
    • In another Zn version, using a pre-prepared dry Zn, a mixture of both γ-adduct and α-adduct with a moderate to very good selectivity was observed for aldehydes and ketones, and the stereochemistry assignment of the γ-adducts was not established due to their decomposition. And only a pre-prepared Zn-Cu couple under acidic condition afforded the α-adducts, see: Rice, L. E, Boston, M. C, Finklea, H. O, Suder, B. J, Frazier, J. O, Hudlicky, T. J. Org. Chem. 1984, 49, 1845
    • (c) In another Zn version, using a pre-prepared dry Zn, a mixture of both γ-adduct and α-adduct with a moderate to very good selectivity was observed for aldehydes and ketones, and the stereochemistry assignment of the γ-adducts was not established due to their decomposition. And only a pre-prepared Zn-Cu couple under acidic condition afforded the α-adducts, see: Rice, L. E.; Boston, M. C.; Finklea, H. O.; Suder, B. J.; Frazier, J. O.; Hudlicky, T. J. Org. Chem. 1984, 49, 1845.
  • 11
    • 37549041279 scopus 로고    scopus 로고
    • A cinnamyl Grignard reagent with acetophenone gave a modest selectivity ds 70530, see ref 3a
    • (d) A cinnamyl Grignard reagent with acetophenone gave a modest selectivity (ds 70530), see ref 3a.
  • 24
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    • Yamamoto, H, Ed, Wiley-VCH: Weinheim, Germany
    • (g) Marshall, J. A. In Lewis Acids in Organic Synthesis; Yamamoto, H., Ed.; Wiley-VCH: Weinheim, Germany, 2000; Vol. 1, p 453.
    • (2000) Lewis Acids in Organic Synthesis , vol.1 , pp. 453
    • Marshall, J.A.1
  • 29
    • 0000926764 scopus 로고    scopus 로고
    • For some innovative reports on In-mediated diastereoselective allylations with unsubstituted allyl halides, see: (a) Lobben, P. C, Paquette, L. A. J. Org. Chem. 1998, 63, 6990
    • For some innovative reports on In-mediated diastereoselective allylations with unsubstituted allyl halides, see: (a) Lobben, P. C.; Paquette, L. A. J. Org. Chem. 1998, 63, 6990.
  • 39
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    • Isomers and their ratio could not be precisely determined
    • (g) Isomers and their ratio could not be precisely determined.
  • 40
    • 28744445551 scopus 로고    scopus 로고
    • For our aimed studies on the stereoselective metal-employed additions to ketones, see: a
    • For our aimed studies on the stereoselective metal-employed additions to ketones, see: (a) Babu, S. A.; Yasuda, M.; Shibata, I.; Baba, A. J. Org. Chem. 2005, 70, 10408.
    • (2005) J. Org. Chem , vol.70 , pp. 10408
    • Babu, S.A.1    Yasuda, M.2    Shibata, I.3    Baba, A.4
  • 44
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    • The stereochemistry of the product 3i was unambiguously established from X-ray analysis.
    • (e) The stereochemistry of the product 3i was unambiguously established from X-ray analysis.
  • 45
    • 33645971287 scopus 로고    scopus 로고
    • During our comprehensive investigations on the In-based stereoselective additions of the substituted allylic halides to simple ketones and alkoxy/hydroxy ketones, recently, a partial report with few examples limited to benzoin and cinnamyl bromide appeared; Kumar, S, Kaur, P, Mittal, A, Singh, P. Tetrahedron 2006, 62, 4018
    • (f) During our comprehensive investigations on the In-based stereoselective additions of the substituted allylic halides to simple ketones and alkoxy/hydroxy ketones, recently, a partial report with few examples limited to benzoin and cinnamyl bromide appeared; Kumar, S.; Kaur, P.; Mittal, A.; Singh, P. Tetrahedron 2006, 62, 4018.
  • 46
    • 37549012126 scopus 로고    scopus 로고
    • The stereochemistries of 6e (syn isomer) and 6g (syn-syn isomer, from benzoinmethyl ether 1i) were unambiguously determined from the X-ray structure analyses. For an analogue compound obtained from the reaction of benzoin and cinnamyl bromide E-geometry, a syn-anti stereochemistry was proposed, see ref 8f
    • (g) The stereochemistries of 6e (syn isomer) and 6g (syn-syn isomer, from benzoinmethyl ether 1i) were unambiguously determined from the X-ray structure analyses. For an analogue compound obtained from the reaction of benzoin and cinnamyl bromide (E-geometry), a syn-anti stereochemistry was proposed, see ref 8f.
  • 49
    • 37549003604 scopus 로고    scopus 로고
    • 1H NMR spectral region,
    • 1H NMR spectral region,
  • 50
    • 37549032691 scopus 로고    scopus 로고
    • In the case of cinnamyl bromide with In also a facile formation of two species in THF-d8-D2O was observed, which indicated that the γ-substituted allyl In species are also stable in aqueous condition. They would be RIn(I) and RIn(III)-type species as already discussed in refs 7d and 8a-c. Based on the observed astonishing diastereoselectivities and strong chelation as the key point; plausibly, a low-valent RIn(I)-type transient species could be projected as very reactive intermediate, see SI
    • 2O was observed, which indicated that the γ-substituted allyl In species are also stable in aqueous condition. They would be RIn(I) and RIn(III)-type species as already discussed in refs 7d and 8a-c. Based on the observed astonishing diastereoselectivities and strong chelation as the key point; plausibly, a low-valent RIn(I)-type transient species could be projected as very reactive intermediate, see SI.
  • 51
    • 37549050505 scopus 로고    scopus 로고
    • As noted in ref 3c about the instability of products in column purification, in our case, the homoallyl alcohols 7g-j/6a-g were stable even after several months. But the products 7a-f were slowly decomposed after several months. We unambiguously assigned the stereochemistry of the γ-adducts 6a-g/7g-j, see SI
    • (c) As noted in ref 3c about the instability of products in column purification, in our case, the homoallyl alcohols 7g-j/6a-g were stable even after several months. But the products 7a-f were slowly decomposed after several months. We unambiguously assigned the stereochemistry of the γ-adducts 6a-g/7g-j, see SI.


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