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Volumn 130, Issue 4, 2008, Pages 1440-1452

Metal-catalyzed 1,2-shift of diverse migrating groups in allenyl systems as a new paradigm toward densely functionalized heterocycles

Author keywords

[No Author keywords available]

Indexed keywords

ALLENYL SYSTEMS; CYCLOISOMERIZATION; FUNCTIONALIZED HETEROCYCLES; REGIODIVERGENT CONDITIONS; SYNTHETIC CHEMISTRY;

EID: 38649108487     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja0773507     Document Type: Article
Times cited : (276)

References (310)
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    • For the cuprate-assisted transformation of propargylic thioacetals into allenyl copper species, see: ref 8c and d.
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    • The more facile propargyl-allenyl isomerization for selenoalkynones is well supported by notable cycloisomerization of 16a under thermal conditions in the absence of base and Cu-catalyst Table 3, entry 4
    • The more facile propargyl-allenyl isomerization for selenoalkynones is well supported by notable cycloisomerization of 16a under thermal conditions in the absence of base and Cu-catalyst (Table 3, entry 4).
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    • It should be noted that involvement of any possible ionization pathways during cycloisomerization of thioalkynones 12 was ruled out by the absence of scrambling for alkyl- and arylthio- groups in crossover experiment
    • It should be noted that involvement of any possible ionization pathways during cycloisomerization of thioalkynones 12 was ruled out by the absence of scrambling for alkyl- and arylthio- groups in crossover experiment.
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    • This is in striking contrast to cycloisomerization of alkynyl imines and ketones, where significant loss of deuterium was observed; see refs 9 and 12
    • This is in striking contrast to cycloisomerization of alkynyl imines and ketones, where significant loss of deuterium was observed; see refs 9 and 12.
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    • Decrease in regioselectivity of deuterium vs bromine migration is explained by the isotope effect analogous to that observed by Hashmi in the Pd-catalyzed cycloisomerization of allenyl ketones; see ref 7s
    • Decrease in regioselectivity of deuterium vs bromine migration is explained by the isotope effect analogous to that observed by Hashmi in the Pd-catalyzed cycloisomerization of allenyl ketones; see ref 7s.
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    • (b) Mamane, V.; Gress, T.; Krause, H.; FUrstner, A. J. Am. Chem. Soc. 2004, 126, 8654. See also refs 8k, 45h, and 48a,b.
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    • For activation of enone moiety by Lewis acids see, for example: (a) Childs, R. F.; Mulholland, D. L.; Nixon, A. Can. J. Chem. 1982, 60, 801.
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    • For examples of 1,2-shift in vinyl cations, see: (a) Capozzi, G.; Lucchini, V.; Marcuzzi, F.; Melloni, G. Tetrahedron Lett. 1976, 17, 717.
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    • See also ref 7q.
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    • 20 from 2-thio- to 3-thiofuran after assembly of the furan core.
    • 20 from 2-thio- to 3-thiofuran after assembly of the furan core.
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    • For Pd-carbenoid species in the synthesis of furans, see ref 7s. For Pd-catalyzed rearrangement see: (a) Rautenstrauch, V, Burger, U, Wirthner, P. Chimia 1985, 39, 225
    • For Pd-carbenoid species in the synthesis of furans, see ref 7s. For Pd-catalyzed rearrangement see: (a) Rautenstrauch, V.; Burger, U.; Wirthner, P. Chimia 1985, 39, 225.
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    • For Au-catalyzed rearrangement, see: (g) Mamane, V.; Gress, T.; Krause, H.; Fürstner, A. J. Am. Chem. Soc. 2004, 126, 8654. See also ref s 8k and 45.
    • For Au-catalyzed rearrangement, see: (g) Mamane, V.; Gress, T.; Krause, H.; Fürstner, A. J. Am. Chem. Soc. 2004, 126, 8654. See also ref s 8k and 45.
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    • The observed migratory aptitude trends (Ph vs. Et, and Ph vs. Me) do not correspond to diose reported in literature for 1,2-alkyl migration to carbenoid center. See, for example: (a) Philip, H.; Keating, J. Tetrahedron Lett. 1961, 2, 523.
    • The observed migratory aptitude trends (Ph vs. Et, and Ph vs. Me) do not correspond to diose reported in literature for 1,2-alkyl migration to carbenoid center. See, for example: (a) Philip, H.; Keating, J. Tetrahedron Lett. 1961, 2, 523.


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