The Direct Organocatalytic Asymmetric Mannich Reaction: Unmodified Aldehydes as Nucleophiles

Journal of Organic Chemistry

Volumn 68, Issue 25, 2003, Pages 9624-9634

  Notz, Wolfgang ^a   Tanaka, Fujie ^a   Watanabe, Shin Ichi ^a   Chowdari, Naidu S ^a   Turner, James M ^a   Thayumanavan, Rajeswari ^a   Barbas III, Carlos F ^a  

^a SCRIPPS RESEARCH INSTITUTE   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

NUCLEOPHILES;

ALCOHOLS; CATALYSTS; NITROGEN COMPOUNDS; SYNTHESIS (CHEMICAL);

ALDEHYDES;

ALDEHYDE; AMINOALCOHOL; BETA LACTAM ANTIBIOTIC; PYRROLIDINE DERIVATIVE;

ARTICLE; CATALYSIS; CHEMICAL MODIFICATION; CHIRALITY; ENANTIOSELECTIVITY; MANNICH REACTION; REACTION ANALYSIS; STEREOCHEMISTRY; SYNTHESIS;

ALDEHYDES; AMINO ACIDS; AMINO ALCOHOLS; CATALYSIS; DIOXANES; IMINES; LACTAMS; MANNICH BASES; MODELS, CHEMICAL; PROLINE; PYRROLIDINES; SOLVENTS; STEREOISOMERISM; STRUCTURE-ACTIVITY RELATIONSHIP;

EID: 0345529038     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo0347359     Document Type: Article

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153. For a preliminary account of these results, see ref 11c.
154. The application of aqueous reaction media allowed for the development of a novel one-pot Mannich/indium-promoted allylation tandem reaction affording γ-lactones, thus providing novel α-amino-γ-lactones with three contiguous stereocenters. See: Córdova, A.; Barbas, C. F., III Tetrahedron Lett. 2003, 44, 1923. For a complete study of the organocatalytic Mannich reaction in ionic liquids see: Chowdari, N. S.; Ramachary, D. B.; Barbas, C. F., III Synlett 2003, 1906.
155. The application of aqueous reaction media allowed for the development of a novel one-pot Mannich/indium-promoted allylation tandem reaction affording γ-lactones, thus providing novel α-amino-γ-lactones with three contiguous stereocenters. See: Córdova, A.; Barbas, C. F., III Tetrahedron Lett. 2003, 44, 1923. For a complete study of the organocatalytic Mannich reaction in ionic liquids see: Chowdari, N. S.; Ramachary, D. B.; Barbas, C. F., III Synlett 2003, 1906.
156. Whereas these products and the Mannich products described herein in general epimerize and racemize, respectively, when stored neatly at room temperature, they can be stored at -25°C in solution (EtOAc) without decomposition, epimerization, and loss of ee.
157. Typically, the syn/anti isomers are an inseparable mixture by preparative column chromatography. However, both the syn and anti isomers could be resolved by analytical HPLC.
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162. Following submission of this paper concerning one-pot three-component Mannich reactions involving aldehydes, Hayashi et al. reported similar results also obtained with proline catalysis: Hayashi, Y.; Tsuboi, W.; Ashimine, I.; Urushima, T.; Shoji, M.; Sakai, K. Angew. Chem., Int. Ed. 2003, 42, 3677.
163. The reaction also proceeded well in other solvents. Dioxane (at 23 °C): 65% yield; dr > 10:1; 99% ee. THF (at 23 °C): 51% yield; dr > 10:1; 99% ee. Ether (at 23 °C): 40% yield; dr > 10:1; 99% ee. THF (at 4 °C): 36% yield; dr > 10:1; >99% ee. Dioxane (at 4 °C): 62% yield; dr > 10:1; 99% ee.
164. We observed that Mannich product 15 was configurationally unstable if stored at room temperature or subjected to silica gel column chromatography. We therefore decided to reduce the aldehyde functionality of 15 with excess NaBH4 prior to isolation and determination of ee.
165. These reactions can be readily performed on a 10 mmol scale with no detrimental effect on yield or enantioselectivity as demonstrated for amino alcohol 16.
166. 4) resulted in improved syn/anti ratios and enantiomeric excesses compared to a direct one-pot reduction protocol. Furthermore, we showed that the Mannich products bearing an aldehyde functionality are slightly prone to epimerization, thus diminishing the syn/anti ratio. This might explain some of the lower selectivities observed (e.g. Table 8, entries 4 and 6).
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169. R = 14.02 min.
170. Very recently, calculations confirmed this stereochemical outcome. See: Bahmanyar, S.; Houk, K. N. Org. Lett. 2003, 5, 1249.
171. Electrostatic interactions have been observed in noncatalytic asymmetric Mannich-type reactions with preformed SMP enamines. See ref 2a and: Vinkovic, V.; Sunjic, V. Tetrahedron 1997, 53, 689.
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178. 2)}.
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185. Carbohydrate-based oximes derived from γ-keto amino acids were recently applied to the synthesis of glycopeptides with clustered oxime-linked glycans. See: Marcaurelle, L. A.; Shin, Y.; Goon, S.; Bertozzi, C. R. Org. Lett. 2001, 3, 3691 and references therein.
186. Although the p-methoxyphenyl group (PMP) was used as the nitrogen protective group throughout our studies, other nitrogen protective groups are also conceivable, particularly in the case of glyoxylate imines. For an example, see: Nakamura, Y.; Matsubara, R.; Kiyohara, H.; Kobayashi, S. Org. Lett. 2003, 5; 2481.
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