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Volumn 75, Issue 16, 2010, Pages 5425-5437

Asymmetric total synthesis of (+)-Hexachlorosulfolipid, a cytotoxin isolated from adriatic mussels

Author keywords

[No Author keywords available]

Indexed keywords

ABSOLUTE CONFIGURATION; ADRIATIC; ASYMMETRIC TOTAL SYNTHESIS; CHIRAL EPOXIDES; CHLORINATED HYDROCARBON; CYTOTOXIC; CYTOTOXINS; ENANTIOSELECTIVE TOTAL SYNTHESIS; IN-SITU; MYTILUS GALLOPROVINCIALIS; TOTAL SYNTHESIS;

EID: 77955703986     PISSN: 00223263     EISSN: 15206904     Source Type: Journal    
DOI: 10.1021/jo100534d     Document Type: Article
Times cited : (55)

References (74)
  • 1
    • 0014097073 scopus 로고
    • For pioneering studies on this class of molecules, see
    • For pioneering studies on this class of molecules, see: Mayers, G. L.; Haines, T. H. Biochemistry 1967, 6, 1665-1671
    • (1967) Biochemistry , vol.6 , pp. 1665-1671
    • Mayers, G.L.1    Haines, T.H.2
  • 19
    • 51949102215 scopus 로고    scopus 로고
    • An elegant methodology was developed by this group
    • An elegant methodology was developed by this group: Shibuya, G. M.; Kanady, J. S.; Vanderwal, C. D. J. Am. Chem. Soc. 2008, 130, 12514-12518
    • (2008) J. Am. Chem. Soc. , vol.130 , pp. 12514-12518
    • Shibuya, G.M.1    Kanady, J.S.2    Vanderwal, C.D.3
  • 20
    • 64249116162 scopus 로고    scopus 로고
    • While the present paper was in review, asymmetric total synthesis of malhamensilipine A was reported:;;;; J. Am. Chem. Soc. 2010, 132, 2542-2543
    • Kanady, J. S.; Nguyen, J. D.; Ziller, J. W.; Vanderwal, C. D. J. Org. Chem. 2009, 74, 2175-2178 While the present paper was in review, asymmetric total synthesis of malhamensilipine A was reported: Bedke, D. K.; Shibuya, G. M.; Pereira, A. R.; Gerwick, W. H.; Vanderwal, C. D. J. Am. Chem. Soc. 2010, 132, 2542-2543
    • (2009) J. Org. Chem. , vol.74 , pp. 2175-2178
    • Kanady, J.S.1    Nguyen, J.D.2    Ziller, J.W.3    Vanderwal, C.D.4    Bedke, D.K.5    Shibuya, G.M.6    Pereira, A.R.7    Gerwick, W.H.8    Vanderwal, C.D.9
  • 21
    • 59049083939 scopus 로고    scopus 로고
    • For the total synthesis of (±)-hexachlorosulfolipid, see:;;, For an account of this work, see:; Nature 2009, 457, 548-549 For related studies, see:;;; J. Am. Chem. Soc. 2009, 131, 15866-15876
    • For the total synthesis of (±)-hexachlorosulfolipid, see: Nilewski, C.; Geisser, R. W.; Carreira, E. M. Nature 2009, 457, 573-576 For an account of this work, see: Bedke, D. K.; Vanderwal, C. D. Nature 2009, 457, 548-549 For related studies, see: Nilewski, C.; Geisser, R. W.; Ebert, M.-O.; Carreira, E. M. J. Am. Chem. Soc. 2009, 131, 15866-15876
    • (2009) Nature , vol.457 , pp. 573-576
    • Nilewski, C.1    Geisser, R.W.2    Carreira, E.M.3    Bedke, D.K.4    Vanderwal, C.D.5    Nilewski, C.6    Geisser, R.W.7    Ebert, M.-O.8    Carreira, E.M.9
  • 25
    • 33645897192 scopus 로고
    • For a pertinent review on the chemistry of allylic 1,3-strain, see
    • For a pertinent review on the chemistry of allylic 1,3-strain, see: Hoffmann, R. W. Chem. Rev. 1989, 89, 1841-1860
    • (1989) Chem. Rev. , vol.89 , pp. 1841-1860
    • Hoffmann, R.W.1
  • 26
    • 0000128751 scopus 로고
    • Chamberlin and co-workers (ref 10a) have reported that 2-iodo-1,3- anti -diols are stereo- and regioselectively produced from 1,2-disubstituted allylic alcohols via an intermediacy of cyclic iodonium ions generated preferentially syn to the allylic hydroxyl group in the 1,3-allylic strain model, followed by their nucleophilic hydration at the sterically more accessible position. This observation suggested that dichlorination of our allylic alcohol substrate 5 would favor the production of undesired (2 S, 3 R)-pentachloride 21
    • Chamberlin and co-workers (ref 10a) have reported that 2-iodo-1,3- anti -diols are stereo- and regioselectively produced from 1,2-disubstituted allylic alcohols via an intermediacy of cyclic iodonium ions generated preferentially syn to the allylic hydroxyl group in the 1,3-allylic strain model, followed by their nucleophilic hydration at the sterically more accessible position. This observation suggested that dichlorination of our allylic alcohol substrate 5 would favor the production of undesired (2 S, 3 R)-pentachloride 21. Chamberlin, A. R.; Mulholland, R. L., Jr. Tetrahedron 1984, 40, 2297-2302
    • (1984) Tetrahedron , vol.40 , pp. 2297-2302
    • Chamberlin, A.R.1    Mulholland Jr., R.L.2
  • 27
    • 0021097053 scopus 로고
    • Other related studies on the diastereoselective halogenation of allylic alcohols, for instance:; J. Org. Chem. 1981, 46, 1227-1229
    • Chamberlin, A. R.; Dezube, M.; Dussault, P.; McMills, M. C. J. Am. Chem. Soc. 1983, 105, 5819-5825 Other related studies on the diastereoselective halogenation of allylic alcohols, for instance: Midland, M. M.; Halterman, R. L. J. Org. Chem. 1981, 46, 1227-1229
    • (1983) J. Am. Chem. Soc. , vol.105 , pp. 5819-5825
    • Chamberlin, A.R.1    Dezube, M.2    Dussault, P.3    McMills, M.C.4    Midland, M.M.5    Halterman, R.L.6
  • 29
    • 0000012312 scopus 로고
    • Morrison J.D., Ed.; Academic Press, Inc.: New York
    • Bartlett, P. A. In Asymmetric Synthesis; Morrison, J. D., Ed.; Academic Press, Inc.: New York, 1984; Vol. 3, pp 411 - 454.
    • (1984) Asymmetric Synthesis , vol.3 , pp. 411-454
    • Bartlett, P.A.1
  • 31
    • 33646465280 scopus 로고    scopus 로고
    • Allylic alcohol 10 was prepared by a four-step protocol similar to the known method; see
    • Allylic alcohol 10 was prepared by a four-step protocol similar to the known method; see: Lu, K.; Huang, M.; Xiang, Z.; Liu, Y.; Chen, J.; Yang, Z. Org. Lett. 2006, 8, 1193-1196
    • (2006) Org. Lett. , vol.8 , pp. 1193-1196
    • Lu, K.1    Huang, M.2    Xiang, Z.3    Liu, Y.4    Chen, J.5    Yang, Z.6
  • 33
    • 84941216140 scopus 로고
    • For reviews, see J. D., Ed.; Academic Press: Orlando
    • For reviews, see: Finn, M. G.; Sharpless, K. B. In Asymmetric Synthesis; Morrison, J. D., Ed.; Academic Press: Orlando, 1985; Vol. 5, p 247 - 308.
    • (1985) Asymmetric Synthesis; Morrison , vol.5 , pp. 247-308
    • Finn, M.G.1    Sharpless, K.B.2
  • 36
    • 0000546031 scopus 로고
    • Trost, B. M.; Fleming, I., Eds.; Pergamon Press: Oxford
    • Johnson, R. A.; Sharpless, K. B. In Comprehensive Organic Synthesis; Trost, B. M.; Fleming, I., Eds.; Pergamon Press: Oxford, 1991; Vol. 7, pp 389 - 436.
    • (1991) Comprehensive Organic Synthesis , vol.7 , pp. 389-436
    • Johnson, R.A.1    Sharpless, K.B.2
  • 51
    • 0542376714 scopus 로고
    • The stereochemistry of dichloride 11 was established by its transformation into (E)-olefin by means of the known reductive olefination protocol.;, For details, see the Supporting Information
    • The stereochemistry of dichloride 11 was established by its transformation into (E)-olefin by means of the known reductive olefination protocol. Sonnet, P. E.; Oliver, J. E. J. Org. Chem. 1976, 41, 3284-3286 For details, see the Supporting Information.
    • (1976) J. Org. Chem. , vol.41 , pp. 3284-3286
    • Sonnet, P.E.1    Oliver, J.E.2
  • 53
    • 77955678774 scopus 로고    scopus 로고
    • Selected reviews for Hosomi-Sakurai reactions Li, J. J., Ed.; John Wiley & Sons: Hoboken, NJ
    • Selected reviews for Hosomi-Sakurai reactions: Biamonte, M. A. In Name Reactions for Homologations; Li, J. J., Ed.; John Wiley & Sons: Hoboken, NJ, 2009; Part 1, pp 539 - 575.
    • (2009) Name Reactions for Homologations , Issue.PART 1 , pp. 539-575
    • Biamonte, M.A.1
  • 54
    • 45249121299 scopus 로고    scopus 로고
    • Yamamoto, H.; Ishihara, K., Eds.; Wiley-VCH Verlag GmbH & Co. KGaA: Weinhem
    • Hosomi, A.; Miura, K. In Acid Catalysis in Modern Organic Synthesis; Yamamoto, H.; Ishihara, K., Eds.; Wiley-VCH Verlag GmbH & Co. KGaA: Weinhem, 2008; Vol. 1, pp 469 - 516.
    • (2008) Acid Catalysis in Modern Organic Synthesis , vol.1 , pp. 469-516
    • Hosomi, A.1    Miura, K.2
  • 56
    • 0001579610 scopus 로고
    • Trost, B. M.; Fleming, I., Eds.; Pergamon Press: Oxford
    • Fleming, I. In Comprehensive Organic Synthesis; Trost, B. M.; Fleming, I., Eds.; Pergamon Press: Oxford, 1991; vol. 6, pp 563 - 593.
    • (1991) Comprehensive Organic Synthesis , vol.6 , pp. 563-593
    • Fleming, I.1
  • 61
    • 33644959351 scopus 로고    scopus 로고
    • For a theoretical investigation of the nucleophilic addition to α-chloroaldehydes, see:;;, For a recent example, see:; Org. Lett. 2007, 9, 5083-5086 and references cited therein
    • For a theoretical investigation of the nucleophilic addition to α-chloroaldehydes, see: Cee, V. J.; Cramer, C. J.; Evans, D. A. J. Am. Chem. Soc. 2006, 128, 2920-2930 For a recent example, see: Kang, B.; Britton, R. Org. Lett. 2007, 9, 5083-5086 and references cited therein
    • (2006) J. Am. Chem. Soc. , vol.128 , pp. 2920-2930
    • Cee, V.J.1    Cramer, C.J.2    Evans, D.A.3    Kang, B.4    Britton, R.5
  • 62
    • 77955698894 scopus 로고    scopus 로고
    • 1H NMR spectra
    • 1H NMR spectra.
  • 63
    • 77955694249 scopus 로고    scopus 로고
    • 3P/hexachloroacetone similarly gave desired trichloride 6 in 74% yield. However, partly because side reactions occurred under this condition, the yields varied when the reactions were performed on a large scale
    • 3P/hexachloroacetone similarly gave desired trichloride 6 in 74% yield. However, partly because side reactions occurred under this condition, the yields varied when the reactions were performed on a large scale.
  • 64
    • 77955692458 scopus 로고    scopus 로고
    • In this case, dichloroethane was used as solvent because of the higher solubility of the reagents and substrate. Dichlorination of epoxide 12 in toluene, however, afforded trichloride 6 in a comparable yield (68%) to that in dichloroethane
    • In this case, dichloroethane was used as solvent because of the higher solubility of the reagents and substrate. Dichlorination of epoxide 12 in toluene, however, afforded trichloride 6 in a comparable yield (68%) to that in dichloroethane.
  • 65
    • 77955680762 scopus 로고    scopus 로고
    • This material was readily prepared by silylating 5-hexen-1-ol with TBDPSCl in the presence of imidazole in DMF (95% yield)
    • This material was readily prepared by silylating 5-hexen-1-ol with TBDPSCl in the presence of imidazole in DMF (95% yield).
  • 67
    • 77955685406 scopus 로고    scopus 로고
    • The stereochemistry of β-alcohol 13a and α-alcohol 13b was determined by their transformation into the corresponding cis - and trans -epoxides, respectively. For details, see the Supporting Information
    • The stereochemistry of β-alcohol 13a and α-alcohol 13b was determined by their transformation into the corresponding cis-and trans -epoxides, respectively. For details, see the Supporting Information.
  • 68
    • 0031592567 scopus 로고    scopus 로고
    • 3) dichlorination protocols have nearly identical levels of efficiency and selectivity. However, we assume that there may be some differences in the Lewis acidities of the two reagent systems, which possibly arise from the chemical species generated in the reaction mixtures
    • 3) dichlorination protocols have nearly identical levels of efficiency and selectivity. However, we assume that there may be some differences in the Lewis acidities of the two reagent systems, which possibly arise from the chemical species generated in the reaction mixtures. Markó, I. E.; Richardson, P. R.; Bailey, M.; Maguire, A. R.; Coughlan, N. Tetrahedron Lett. 1997, 38, 2339-2342
    • (1997) Tetrahedron Lett. , vol.38 , pp. 2339-2342
    • Markó, I.E.1    Richardson, P.R.2    Bailey, M.3    Maguire, A.R.4    Coughlan, N.5
  • 70
    • 77955689300 scopus 로고    scopus 로고
    • Compound 19 was possibly produced by the neighboring participation of the trichloroacetyl group followed by the elimination. Its stereochemistry at the 3 position has, however, yet to be determined
    • Compound 19 was possibly produced by the neighboring participation of the trichloroacetyl group followed by the elimination. Its stereochemistry at the 3 position has, however, yet to be determined.
  • 72
    • 77955706333 scopus 로고    scopus 로고
    • We currently assume that the low energy gap observed between the two conformers a and b may arise from the relative instability of conformer a that suffers from steric interaction between the hydrogen atom at C3 position and the chlorine atom at C5. The interaction increases the relative energy of conformer a, leading to the proximity in the conformational energy gap of the two possible conformers
    • We currently assume that the low energy gap observed between the two conformers a and b may arise from the relative instability of conformer a that suffers from steric interaction between the hydrogen atom at C3 position and the chlorine atom at C5. The interaction increases the relative energy of conformer a, leading to the proximity in the conformational energy gap of the two possible conformers.
  • 73
    • 77955670925 scopus 로고    scopus 로고
    • In this case, however, the observed stereochemical outcome may possibly indicate an intermediacy of the coordination of a Lewis acidic reagent to the hydroxyl group, such as the trimethylsilylated manganese complex, (22) which prevents substrate 5 from forming a β-chloronium intermediate as in the case of substrate 14, eventually leading to (2 R, 3 S)-pentachloride 20 as the major product. We are currently making further efforts to elucidate the origin of this stereochemical preference
    • In this case, however, the observed stereochemical outcome may possibly indicate an intermediacy of the coordination of a Lewis acidic reagent to the hydroxyl group, such as the trimethylsilylated manganese complex, (22) which prevents substrate 5 from forming a β-chloronium intermediate as in the case of substrate 14, eventually leading to (2 R, 3 S)-pentachloride 20 as the major product. We are currently making further efforts to elucidate the origin of this stereochemical preference.


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