Highly enantioselective catalytic acyl-Pictet-Spengler reactions

Journal of the American Chemical Society

Volumn 126, Issue 34, 2004, Pages 10558-10559

  Taylor, Mark S ^a   Jacobsen, Eric N ^a  

^a HARVARD UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

BORON DERIVATIVE; CARBOLINE DERIVATIVE; INDOLE ALKALOID; LEWIS ACID; N ACETYL BETA CARBOLINE DERIVATIVE; NITRONE DERIVATIVE; REAGENT; TETRAHYDROISOQUINOLINE DERIVATIVE; THIOUREA DERIVATIVE; TRYPTOLINE; UNCLASSIFIED DRUG;

ARTICLE; CATALYSIS; CATALYST; CHEMICAL INTERACTION; CHEMICAL STRUCTURE; CHIRALITY; CYCLIZATION; DIASTEREOISOMER; ENANTIOSELECTIVITY; HYDROGEN BOND; PICTET SPENGLER REACTION; POLYMERIZATION; REACTION ANALYSIS; STOICHIOMETRY; STRUCTURE ANALYSIS; SUBSTITUTION REACTION; SYNTHESIS; TECHNIQUE;

CARBOLINES; CATALYSIS; CYCLIZATION; HYDROGEN BONDING; IMINES; INDOLE ALKALOIDS; STEREOISOMERISM; THIOUREA;

EID: 4344713238     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja046259p     Document Type: Article

References (48)

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43. Acylating agents screened included acyl halides, anhydrides, and chloroformates.
44. Majority of solvents tested (toluene, dichloromethane, tetrahydrofuran) afforded poor enantioselectivity. Other ethereal solvents such as tert-butyl methyl ether and diisopropyl ether provided comparable but slightly inferior results to diethyl ether. Temperature optimization was required to suppress competing uncatalyzed cyclization.
45. A variety of (R,R)-2-pyrrolylcyctohexylamines was prepared in good yield by Paal-Knorr condensation of diaminocyclohexane and 1,4-diketones (1.0 equiv). See Supporting Information for details.
46. Use of catalyst 1e provides products 3d and 3e (Table 2) in 89 and 84% ee, respectively.
47. Catalyst 1f may be recovered in quantitative yield by chromatography and reused to produce 3a without deterioration of cyclization yield or enantiomeric excess. See Supporting Information for details.
48. Catalyst undergoes decomposition by acetylation of the thiourea moiety at the temperatures required for efficient cyclization of such substrates, resulting in low enantioselectivity.