Use of a New Spirophosphine To Achieve Catalytic Enantioselective [4 + 1] Annulations of Amines with Allenes To Generate Dihydropyrroles

Journal of the American Chemical Society

Volumn 137, Issue 11, 2015, Pages 3803-3806

  Kramer, Soren ^a   Fu, Gregory C ^a  

^a California Institute of Technology   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ENANTIOSELECTIVITY; PHOSPHORUS COMPOUNDS; STEREOCHEMISTRY; SYNTHESIS (CHEMICAL);

ALLENES; BIOACTIVE MOLECULES; DIHYDROPYRROLE; ENANTIOSELECTIVE; ENANTIOSELECTIVE SYNTHESIS; NITROGEN HETEROCYCLES;

HYDROCARBONS;

ALLENE DERIVATIVE; AMINE; DIHYDROPYRROLE DERIVATIVE; PHOSPHINE DERIVATIVE; PYRROLE; SPIROPHOSPHINE; UNCLASSIFIED DRUG; ALKADIENE; PROPADIENE; PYRROLE DERIVATIVE;

ARTICLE; CATALYSIS; CHEMICAL STRUCTURE; ENANTIOSELECTIVITY; STEREOCHEMISTRY; SYNTHESIS; CHEMISTRY;

ALKADIENES; AMINES; CATALYSIS; PHOSPHINES; PYRROLES;

EID: 84926166328     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/jacs.5b01944     Document Type: Article

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27. After exposure to air as a solid in an open vial for 30 days, no decomposition or oxidation of phosphine 1 was detected by 31P or 1H NMR spectroscopy; after 5 months under these conditions, a small amount (∼3%) of the phosphine oxide was observed. After exposure to air in solution (CPME:toluene 1:1, "sparged" with air) for 24 h, ∼20% of the phosphine oxide was observed.
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35. The use of carboxylate leaving groups other than acetate led to essentially identical ee and to either slightly (benzoate and pivalate) or considerably (trichloroacetate) lower yield.
36. During the course of a [4 + 1] annulation, the ee of the unreacted allene was low (<10%).
37. If enantioenriched allene is subjected to the annulation conditions, essentially no racemization of the allene is observed at partial conversion.
38. Because of the heterogeneity of the reaction mixture, due to the relatively low solubility of the sulfonamides in CPME:toluene, we have not been able to perform meaningful kinetics and relative-reactivity studies.