Palladium-catalyzed asymmetric conjugate addition of arylboronic acids to five-, six-, and seven-membered β-substituted cyclic enones: enantioselective construction of all-carbon quaternary stereocenters

Journal of the American Chemical Society

Volumn 133, Issue 18, 2011, Pages 6902-6905

  Kikushima, Kotaro ^a   Holder, Jeffrey C ^a   Gatti, Michele ^a   Stoltz, Brian M ^a  

^a California Institute of Technology   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ARYLBORONIC ACIDS; ASYMMETRIC CONJUGATE ADDITION; BENZYLIC; ENANTIOSELECTIVE; ENANTIOSELECTIVE CONSTRUCTION; QUATERNARY STEREOCENTERS; SIMPLE METHOD; STEREOCENTERS;

CATALYSIS;

ARYLBORINIC ACID; BENZYL DERIVATIVE; BORINIC ACID DERIVATIVE; CYCLIC ENONE DERIVATIVE; KETONE DERIVATIVE; OXAZOLINE DERIVATIVE; PALLADIUM; PYRIDINOOXAZOLINE; UNCLASSIFIED DRUG;

ADDITION REACTION; ARTICLE; CATALYSIS; CHEMICAL STRUCTURE; CONJUGATION; ENANTIOSELECTIVITY; STEREOISOMERISM; SYNTHESIS;

BORONIC ACIDS; CATALYSIS; CYCLOHEXANONES; ORGANOMETALLIC COMPOUNDS; PALLADIUM;

EID: 79955703521     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/ja200664x     Document Type: Article

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56. 18
57. Although the reactions are generally high yielding, the impurity profile is dominated by homocoupling of the arylboronic acid to the corresponding biaryl.
58. To date, reactions involving either heteroarylboronic acids or β-aryl substituted enones have been unsuccessful.
59. We have conducted the Pd-catalyzed reaction of PhB(OH)2 with racemic bicyclic enone (±)-i, under our standard conditions (Ph-B(OH)2 (2 equiv), 4 (6 mol %), Pd(OCOCF3)2 (5 mol %), ClCH2CH2Cl, 60 °C, 12 h). This process results in a modest kinetic resolution of the starting enone (krel(fast/slow) = 3.4, (-)-i isolated in 95% ee at 89% conversion).