Phosphine-Catalyzed Enantioselective Intramolecular [3+2] Annulations to Generate Fused Ring Systems

Journal of the American Chemical Society

Volumn 137, Issue 13, 2015, Pages 4587-4591

  Lee, Sarah Yunmi ^a,b   Fujiwara, Yuji ^b   Nishiguchi, Atsuko ^a,b   Kalek, Marcin ^a   Fu, Gregory C ^a,b  

^a California Institute of Technology   (United States)

^b MASSACHUSETTS INSTITUTE OF TECHNOLOGY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CATALYSIS; HYDROCARBONS; SCAFFOLDS; STEREOCHEMISTRY;

ASYMMETRIC VARIANTS; BIOACTIVE COMPOUNDS; CHEMICAL EQUATIONS; ENANTIOSELECTIVE; FUSED-RING SYSTEM; INTRAMOLECULAR PROCESS; MECHANISTIC STUDIES; [3+2]-CYCLOADDITION;

PHOSPHORUS COMPOUNDS;

ALKENE; COUMARIN DERIVATIVE; DIQUINANE DERIVATIVE; FUSED RINGS WITH THREE OR MORE HETERO ATOMS; PHOSPHINE; QUINOLIN 2 ONE DERIVATIVE; UNCLASSIFIED DRUG; FUSED HETEROCYCLIC RINGS; PHOSPHINE DERIVATIVE;

ARTICLE; ASYMMETRIC CATALYSIS; ASYMMETRIC SYNTHESIS; CATALYSIS; CATALYST; CHEMICAL STRUCTURE; CONFORMATION; CYCLOADDITION; DIASTEREOISOMER; ENANTIOMER; ENANTIOSELECTIVITY; NUCLEOPHILICITY; PROTON NUCLEAR MAGNETIC RESONANCE; STEREOCHEMISTRY; STEREOISOMERISM; CHEMISTRY;

ALKENES; BRIDGED BICYCLO COMPOUNDS, HETEROCYCLIC; CATALYSIS; PHOSPHINES; STEREOISOMERISM;

EID: 84926644385     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/jacs.5b01985     Document Type: Article

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29. A negative ee value signifies that the major annulation product is the enantiomer of A.
30. Notes: For entry 1 of Table 1, the ee of the product is constant throughout the annulation.
31. A preliminary attempt to apply our standard conditions to the corresponding synthesis of a hydrindane was not successful.
32. For the determination of the relative and absolute configuration of the various reaction products, see the Supporting Information.
33. In contrast, α,β-unsaturated esters were not suitable reaction partners in Krische's P(n -Bu)3-catalyzed intramolecular [3+2] annulation (ref 8a).
34. To the best of our knowledge, there has been only one report of an intramolecular Lu annulation of a substrate wherein the olefin is trisubstituted (ref 8b).
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36. Abilify is an example of a bioactive compound that includes a quinolin-2-one subunit.
37. We are aware of one previous report of kinetic resolution in a Lu [3+2] annulation, an intermolecular coupling with s ∼ 1.3 (ref 5b).
38. Notes: The ee of the product is independent of the enantiomeric purity of the allene.
39. The reaction of an enantioenriched allene with an achiral phosphine led to racemic product.
40. We have examined the rate law, employing enantioenriched (the more reactive enantiomer), rather than racemic, starting material, to avoid complications due to the divergent reactivity of the two enantiomers. The rate law is first order in the catalyst and ∼first order in the substrate. No racemization of the enantioenriched substrate is observed during the course of these kinetics studies.
41. This is consistent with Krische's observations for a P(n -Bu)3-catalyzed intra molecular cycloaddition (ref 8b) and stands in contrast to the stepwise pathway that has been suggested for inter molecular annulations (ref 7).