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Volumn 133, Issue 4, 2011, Pages 736-739

Erratum: Formation of vinyl-, vinylhalide- or acyl-substituted quaternary carbon stereogenic centers through nhc-cu-catalyzed enantioselective conjugate additions of si-containing vinylaluminums to î-substituted cyclic enones (Journal of the American Chemical Society (2011) 133 (736-739) DOI:10.1021/ja110054q);Formation of vinyl-, vinylhalide-or acyl-substituted quaternary carbon stereogenic centers through NHC-Cu-catalyzed enantioselective conjugate additions of Si-containing vinylaluminums to β-substituted cyclic enones

Author keywords

[No Author keywords available]

Indexed keywords

ADDITION REACTIONS; CARBON; ENANTIOSELECTIVITY; HYDROCARBONS; KETONES;

EID: 79851474806     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/ja506298x     Document Type: Erratum
Times cited : (107)

References (53)
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    • For examples of ECA reactions that involve alkylmetal reagents and afford quaternary carbon stereogenic centers, see: (a) Wu, J.; Mampreian, D. M.; Hoveyda, A. H. J. Am. Chem. Soc. 2005, 127, 4584.
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    • For catalytic ECA of vinylzirconiums and silanes, respectively, which afford tertiary C-C bonds, see: a
    • For catalytic ECA of vinylzirconiums and silanes, respectively, which afford tertiary C-C bonds, see: (a) Nicolaou, K. C.; Tang, W.; Dagneau, P.; Faraoni, R. Angew. Chem., Int. Ed. 2005, 44, 3874.
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    • For three examples of ECA reactions of vinylaluminum reagents to β-methylcyclohexenone affording products in 75:25-91:9 er, see: a
    • For three examples of ECA reactions of vinylaluminum reagents to β-methylcyclohexenone affording products in 75:25-91:9 er, see: (a) Vuagnoux-d'Augustin, M.; Alexakis, A. Chem.-Eur. J. 2007, 13, 9647.
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    • Such chiral complexes have been utilized in enantioselective allylic substitutions with vinylaluminum reagents. See
    • Such chiral complexes have been utilized in enantioselective allylic substitutions with vinylaluminum reagents. See: Akiyama, K.; Gao, F.; Hoveyda, A. H. Angew. Chem., Int. Ed. 2010, 49, 419.
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    • For previous applications of catalytic ECA reactions (affording quaternary carbon stereogenic centers) to natural product synthesis, see: (a) Peese, K. M.; Gin, D. Y. Chem.-Eur. J. 2008, 14, 1654.
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    • For determination of the absolute stereochemistry of the ECA products, see the Supporting Information
    • For determination of the absolute stereochemistry of the ECA products, see the Supporting Information.
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    • i-Bu addition product 8 is generated through an NHC-Cu-catalyzed process in 89:11 er. See ref 2h
    • The i-Bu addition product (8) is generated through an NHC-Cu-catalyzed process in 89:11 er. See ref 2h.
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    • opposite sense of absolute stereochemistry observed with sulfonate-containing Cu complexes derived from 2 and 3a-c entries 2-5, Table 1, vs those obtained through phenoxy-based 1 entry 1 or monodentate 4 entry 6, might be due to their unique stereochemical characteristics. Structural studies indicate that, unlike the bridging aryloxide in 1 or monodentate carbenes such as those obtained via 4 and 5, the sulfonate in such chiral Cu complexes is oriented syn to the neighboring Ph group of the NHC backbone. See
    • The opposite sense of absolute stereochemistry observed with sulfonate-containing Cu complexes derived from 2 and 3a-c (entries 2-5, Table 1), vs those obtained through phenoxy-based 1 (entry 1) or monodentate 4 (entry 6), might be due to their unique stereochemical characteristics. Structural studies indicate that, unlike the bridging aryloxide in 1 or monodentate carbenes such as those obtained via 4 and 5, the sulfonate in such chiral Cu complexes is oriented syn to the neighboring Ph group of the NHC backbone. See: Lee, Y.; Li, B.; Hoveyda, A. H. J. Am. Chem. Soc. 2009, 131, 11625.
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    • Preliminary studies indicate that, under the same conditions, NHC-Cu-catalyzed addition of nonsilyl-containing β-vinylaluminum reagents proceeds with equal efficiency but lower enantioselectivity e.g., 19 in 65:35 er and with the same sense of absolute stereochemistry. Investigations regarding identification of catalysts and conditions that promote such processes with high efficiency and enantioselectivity are in progress and will be reported in due course
    • Preliminary studies indicate that, under the same conditions, NHC-Cu-catalyzed addition of nonsilyl-containing β-vinylaluminum reagents proceeds with equal efficiency but lower enantioselectivity (e.g., 19 in 65:35 er) and with the same sense of absolute stereochemistry. Investigations regarding identification of catalysts and conditions that promote such processes with high efficiency and enantioselectivity are in progress and will be reported in due course.
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    • Rccardiphenol B has previously been synthesized by a 12-step sequence through utilization of a chiral auxiliary-based process. See: a, For preparation ofanalogues in the racemic form, see
    • Rccardiphenol B has previously been synthesized by a 12-step sequence through utilization of a chiral auxiliary-based process. See: (a) Tori, M.; Hamaguchi, T.; Sagawa, K.; Sono, M.; Asakawa, Y. J. Org. Chem. 1996, 61, 5362. For preparation ofanalogues in the racemic form, see:
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    • Treatment of the Li-enolate derived from 22 with the appropriately substituted benzyl bromide leads to <2% of the desired alkylation product. In contrast, when benzyl bromide is used, the desired product is obtained in 74% yield >20:1 dr. The above findings suggest that subtle structural alterations of the electrophile can inhibit reaction of the sterically congested enolate. The stereochemical identity of the alkylation product >98% dr is projected on the basis of steric factors and has not been rigorously determined
    • Treatment of the Li-enolate derived from 22 with the appropriately substituted benzyl bromide leads to <2% of the desired alkylation product. In contrast, when benzyl bromide is used, the desired product is obtained in 74% yield (>20:1 dr). The above findings suggest that subtle structural alterations of the electrophile can inhibit reaction of the sterically congested enolate. The stereochemical identity of the alkylation product (>98% dr) is projected on the basis of steric factors and has not been rigorously determined.


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