메뉴 건너뛰기




Volumn 130, Issue 37, 2008, Pages 12514-12518

Stereoselective dichlorination of allylic alcohol derivatives to access key stereochemical arrays of the chlorosulfolipids

Author keywords

[No Author keywords available]

Indexed keywords

ALLYLIC ALCOHOLS; HIGH SELECTIVITY; NATURAL PRODUCTS; STEREO-SELECTIVE; STEREOTETRAD;

EID: 51949102215     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja804167v     Document Type: Article
Times cited : (79)

References (60)
  • 1
    • 4944226169 scopus 로고    scopus 로고
    • The status of organohalogen natural product isolation has been consistently monitored by Professor Gordon W. Gribble:(a) Gribble, G. W. J. Chem. Educ. 2004, 81, 1441-1449
    • The status of organohalogen natural product isolation has been consistently monitored by Professor Gordon W. Gribble:(a) Gribble, G. W. J. Chem. Educ. 2004, 81, 1441-1449.
  • 2
    • 34147164504 scopus 로고    scopus 로고
    • (b) Gribble, G. W. Am. Sci. 2004, 92, 342-349.
    • (2004) Am. Sci , vol.92 , pp. 342-349
    • Gribble, G.W.1
  • 5
    • 51949107007 scopus 로고    scopus 로고
    • From 1995 through 2002, Professor Gribble frequently reviewed the literature pertaining to the isolation of organochlorine natural products. The results were published on the internet in a series of 18 Natural Chlorine Updates. See: http://www.eurochlor.org/index.asp?page=84, accessed June 2, 2008.
    • (e) From 1995 through 2002, Professor Gribble frequently reviewed the literature pertaining to the isolation of organochlorine natural products. The results were published on the internet in a series of 18 "Natural Chlorine Updates". See: http://www.eurochlor.org/index.asp?page=84, accessed June 2, 2008.
  • 6
    • 0033790769 scopus 로고    scopus 로고
    • For several breakthrough examples of catalytic asymmetric α-chlorination of carbonyl compounds, see:a
    • For several breakthrough examples of catalytic asymmetric α-chlorination of carbonyl compounds, see:(a) Hintermann, L.; Togni, A. Helv. Chim. Acta 2000, 83, 2425-2435.
    • (2000) Helv. Chim. Acta , vol.83 , pp. 2425-2435
    • Hintermann, L.1    Togni, A.2
  • 11
    • 0002049209 scopus 로고    scopus 로고
    • For representative chiral auxiliary- and reagent-based protocols for stereoselective introduction of chlorine, see:(a) Evans, D. A, Sjogren, E. B, Weber, A. E, Conn, R. E. Tetrahedron Lett. 1987, 28, 39-42
    • For representative chiral auxiliary- and reagent-based protocols for stereoselective introduction of chlorine, see:(a) Evans, D. A.; Sjogren, E. B.; Weber, A. E.; Conn, R. E. Tetrahedron Lett. 1987, 28, 39-42.
  • 15
    • 51949096689 scopus 로고    scopus 로고
    • There have been innumerable reports of the introduction of single chloride-bearing stereogenic centers using alcohol to chloride conversion protocols
    • There have been innumerable reports of the introduction of single chloride-bearing stereogenic centers using alcohol to chloride conversion protocols.
  • 27
    • 0000573595 scopus 로고    scopus 로고
    • A survey of the distribution of chlorosulfolipids among 30 species of algae has shown that these chlorosulfolipids are present in a significant number of freshwater algae. See:Mercer, E. I.; Davies, C. L. Phytochemistry 1979, 18, 457-462.
    • A survey of the distribution of chlorosulfolipids among 30 species of algae has shown that these chlorosulfolipids are present in a significant number of freshwater algae. See:Mercer, E. I.; Davies, C. L. Phytochemistry 1979, 18, 457-462.
  • 29
    • 0036119159 scopus 로고    scopus 로고
    • Increasingly common occurrences of halogenated fatty acids in a variety of organisms have prompted a review article on the subject: Dembitsky, V. M, Srebnik, M. Prog. Lipid Res. 2002, 41, 315-367
    • Increasingly common occurrences of halogenated fatty acids in a variety of organisms have prompted a review article on the subject: Dembitsky, V. M.; Srebnik, M. Prog. Lipid Res. 2002, 41, 315-367.
  • 32
    • 12944322661 scopus 로고    scopus 로고
    • O'Hagan and coworkers have pioneered the stereocontrolled synthesis of polyfluorinated alkanes with three or four adjacent fluorine-bearing stereogenic centers. For details, and a discussion of the conformations of these interesting polyfluorides, see: a
    • O'Hagan and coworkers have pioneered the stereocontrolled synthesis of polyfluorinated alkanes with three or four adjacent fluorine-bearing stereogenic centers. For details, and a discussion of the conformations of these interesting polyfluorides, see: (a) Nicoletti, M.; O'Hagan, D.; Slawin, A. M. Z. J. Am. Chem. Soc. 2005, 127, 482-483.
    • (2005) J. Am. Chem. Soc , vol.127 , pp. 482-483
    • Nicoletti, M.1    O'Hagan, D.2    Slawin, A.M.Z.3
  • 35
    • 51949108199 scopus 로고    scopus 로고
    • In our work focusing on the chlorosulfolipids, we wish to avoid the potentially problematic conversion of acyclic polyols into the corresponding polychlorides; this procedure could suffer from serious issues of regiocontrol as targets 1-5 bear a mixture of chlorides and hydroxyl/sulfate groups, and potential problems of partial retention in the chlorination reactions would be devastating. In the context of hexapyranose sugars, some beautiful work for the conversion of multiple hydroxyl groups into chlorides, with inversion, has been reported:(a) Jennings, H. J, Jones, J. K. N. Can. J. Chem. 1965, 43, 2372-2385
    • In our work focusing on the chlorosulfolipids, we wish to avoid the potentially problematic conversion of acyclic polyols into the corresponding polychlorides; this procedure could suffer from serious issues of regiocontrol as targets 1-5 bear a mixture of chlorides and hydroxyl/sulfate groups, and potential problems of partial retention in the chlorination reactions would be devastating. In the context of hexapyranose sugars, some beautiful work for the conversion of multiple hydroxyl groups into chlorides, with inversion, has been reported:(a) Jennings, H. J.; Jones, J. K. N. Can. J. Chem. 1965, 43, 2372-2385.
  • 37
    • 0030883527 scopus 로고    scopus 로고
    • For state-of-the-art enantioselective syntheses of propargylic alcohols, which can be reduced to either the (E)- or (Z)-allylic alcohols, see:(a) Matsumura, K.; Hashiguchi, S.; Ikariya, T.; Noyori, R. J. Am. Chem. Soc. 1997, 119, 8738-8739.
    • For state-of-the-art enantioselective syntheses of propargylic alcohols, which can be reduced to either the (E)- or (Z)-allylic alcohols, see:(a) Matsumura, K.; Hashiguchi, S.; Ikariya, T.; Noyori, R. J. Am. Chem. Soc. 1997, 119, 8738-8739.
  • 39
    • 84987584214 scopus 로고    scopus 로고
    • For a seminal contribution in the area of direct enantioenriched (E)- allylic alcohol synthesis, see: Oppolzer, W.; Radinov, R. N. Helv. Chim. Acta 1992, 75, 170-173.
    • For a seminal contribution in the area of direct enantioenriched (E)- allylic alcohol synthesis, see: Oppolzer, W.; Radinov, R. N. Helv. Chim. Acta 1992, 75, 170-173.
  • 40
    • 37549059608 scopus 로고    scopus 로고
    • For direct syntheses of enantioenriched (Z)-allylic alcohols, see: Salvi, L.; Jeon, S.-J.; Fisher, E. L.; Carroll, P. J.; Walsh, P. J. J. Am. Chem. Soc. 2007, 129, 16119-16125.
    • For direct syntheses of enantioenriched (Z)-allylic alcohols, see: Salvi, L.; Jeon, S.-J.; Fisher, E. L.; Carroll, P. J.; Walsh, P. J. J. Am. Chem. Soc. 2007, 129, 16119-16125.
  • 41
    • 0001632904 scopus 로고    scopus 로고
    • Studies of related processes, including dibromination, haloetherification, halolactonization, and selenofunctionalization of alkenes have all been studied in some detail. For some representative examples, see:(a) Liotta, D.; Zima, G.; Saindane, M. J. Org. Chem. 1982, 47, 1258-1267.
    • Studies of related processes, including dibromination, haloetherification, halolactonization, and selenofunctionalization of alkenes have all been studied in some detail. For some representative examples, see:(a) Liotta, D.; Zima, G.; Saindane, M. J. Org. Chem. 1982, 47, 1258-1267.
  • 44
    • 0000012312 scopus 로고
    • Morrison, J. D, Ed, Academic Press, Inc, New York
    • (d) 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
  • 46
    • 0006698496 scopus 로고    scopus 로고
    • The significantly different behavior among the halides and related reagents means that previously studied stereoselective halogenation/ halofunctionalization reactions of allylic alcohols do not necessarily translate to the corresponding dichlorination process. High selectivities in the selenofunctionalization of allylic alcohols are thought to derive from Se-O attractive interactions; analogous interactions are not likely to be operative in chlorination reactions. For an excellent study of the diastereoselective dibromination of chiral allylic alcohols, which resulted in high levels of selectivity in alcoholic solvents with an excess of added bromide ion, see:(a) Midland, M. M, Halterman, R. L. J. Org. Chem. 1981, 46, 1227-1229. Attempts to adapt this procedure with the chlorine equivalent Et 4NCl3 in alcoholic solvents, with added chloride, led to predominant chloroetherification and apparent low selectivity in the small amount of dichlorin
    • 3 in alcoholic solvents, with added chloride, led to predominant chloroetherification and apparent low selectivity in the small amount of dichlorinated product observed.
  • 47
    • 33645897192 scopus 로고
    • For an excellent review, see:a
    • For an excellent review, see:(a) Hoffmann, R. W. Chem. Rev 1989, 89, 1841-1860.
    • (1989) Chem. Rev , vol.89 , pp. 1841-1860
    • Hoffmann, R.W.1
  • 48
    • 0018425810 scopus 로고    scopus 로고
    • 1,3-strain minimization for acyclic stereocontrol in natural product synthesis, see the first synthesis of monensin by Kishi and coworkers: (b) Schmid, G.; Fukuyama, T.; Akasaka, K.; Kishi, Y. J. Am. Chem. Soc. 1979, 101, 259-260.
    • 1,3-strain minimization for acyclic stereocontrol in natural product synthesis, see the first synthesis of monensin by Kishi and coworkers: (b) Schmid, G.; Fukuyama, T.; Akasaka, K.; Kishi, Y. J. Am. Chem. Soc. 1979, 101, 259-260.
  • 50
    • 0026071213 scopus 로고    scopus 로고
    • An earlier variant of this protocol used oxalyl chloride as a chlorine source and generated a thermally unstable reagent of unknown structure that lost chlorination activity above -35°C: (a) Markó, I. E, Richardson, P. F. Tetrahedron Lett. 1991, 32, 1831-1834
    • An earlier variant of this protocol used oxalyl chloride as a chlorine source and generated a thermally unstable reagent of unknown structure that lost chlorination activity above -35°C: (a) Markó, I. E.; Richardson, P. F. Tetrahedron Lett. 1991, 32, 1831-1834.
  • 54
    • 51949110543 scopus 로고    scopus 로고
    • In ref 21, the Markó-Maguire reagent is also reported to open epoxides to the corresponding chlorohydrins and oxidize sufides to sulfoxides. We have not evaluated the reactivity of the Mioskowski reagent in these transformations, as the presence of manganese salt byproducts in the former procedure might well be critical
    • In ref 21, the Markó-Maguire reagent is also reported to open epoxides to the corresponding chlorohydrins and oxidize sufides to sulfoxides. We have not evaluated the reactivity of the Mioskowski reagent in these transformations, as the presence of manganese salt byproducts in the former procedure might well be critical.
  • 55
    • 0004274173 scopus 로고
    • Discovery of the Elements
    • As an important historical note, Scheele's discovery of molecular chlorine resulted from the oxidation of chloride ion by manganese oxides. See:, 3rd ed, Easton, PA
    • As an important historical note, Scheele's discovery of molecular chlorine resulted from the oxidation of chloride ion by manganese oxides. See: Weeks, M. E. Discovery of the Elements, 3rd ed.; Journal of Chemical Education: Easton, PA, 1935; pp 253-257.
    • (1935) Journal of Chemical Education , pp. 253-257
    • Weeks, M.E.1
  • 56
    • 51949089610 scopus 로고    scopus 로고
    • Et4NCl3 effects smooth anti dichlorination of alkynes (ref 23, We have found that the Markó-Maguire reagent performs the same transformation. This is also consistent with these reagents being similar in nature and argues against a possible mechanism involving syn chloromanganation of the π-system, followed by invertive SN2 displacement of manganese by chloride see reference 22a, in the case of alkyne substrates, SN2 displacement on an sp2 carbon would need to be invoked
    • 2 carbon would need to be invoked.
  • 57
    • 51949092837 scopus 로고    scopus 로고
    • Please see the Supporting Information for details
    • Please see the Supporting Information for details.
  • 58
    • 36849010691 scopus 로고    scopus 로고
    • For a recent account of highly stereroselective alkynyllithium additions to α-chloroaldehydes, see
    • For a recent account of highly stereroselective alkynyllithium additions to α-chloroaldehydes, see: Kang, B.; Britton, R. Org. Lett. 2007, 9, 5083-5086.
    • (2007) Org. Lett , vol.9 , pp. 5083-5086
    • Kang, B.1    Britton, R.2
  • 59
    • 33644959351 scopus 로고    scopus 로고
    • The addition of organometallic nucleophiles to a-chloroaldehydes generally proceeds to afford the anti product, consistent with the polar Felkin-Anh model (hyperconjugative stabilization of the transition state/steric control, though the Cornforth model (dipole minimization/steric control) also accounts for the stereochemistry of the products. For an excellent discussion and lead reference, see: Cee, V. J, Cramer, C. J, Evans, D. A. J. Am. Chem. Soc. 2006, 128, 2920-2930
    • The addition of organometallic nucleophiles to a-chloroaldehydes generally proceeds to afford the anti product, consistent with the polar Felkin-Anh model (hyperconjugative stabilization of the transition state/steric control), though the Cornforth model (dipole minimization/steric control) also accounts for the stereochemistry of the products. For an excellent discussion and lead reference, see: Cee, V. J.; Cramer, C. J.; Evans, D. A. J. Am. Chem. Soc. 2006, 128, 2920-2930.
  • 60
    • 0032564684 scopus 로고    scopus 로고
    • For one example of the determination of halohydrin relative stereochemistry by stereospecific conversion to the corresponding epoxides, see:(a) Besse, P.; Sokoltchik, T.; Veschambre, H. Tetrahedron: Asymmetry 1998, 9, 4441-4457. See also refs 3c,d, and 29.
    • For one example of the determination of halohydrin relative stereochemistry by stereospecific conversion to the corresponding epoxides, see:(a) Besse, P.; Sokoltchik, T.; Veschambre, H. Tetrahedron: Asymmetry 1998, 9, 4441-4457. See also refs 3c,d, and 29.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.