TY - JOUR
T1 - Palladium-Catalyzed Suzuki-Miyaura, Heck and Hydroarylation Reactions on (-)-Levoglucosenone and Application to the Synthesis of Chiral γ-Butyrolactones
AU - Stockton, Kieran P.
AU - Merritt, Christopher J.
AU - Sumby, Christopher J.
AU - Greatrex, Ben W.
N1 - Publisher Copyright:
© 2015 Wiley-VCH Verlag GmbH andCo. KGaA, Weinheim.
PY - 2015/11/1
Y1 - 2015/11/1
N2 - The chiral pool material (-)-levoglucosenone (6,8-dioxabicyclo[3.2.1]oct-2-en-4-one, LGO) has been substituted by using a series of Pd-mediated cross-coupling reactions. Iodination of LGO followed by Suzuki-Miyaura cross-coupling reaction with boronic acids by employing the Buchwald ligand SPhos with Pd(OAc)2 afforded 3-aryl derivatives in excellent yields. Selective Heck arylation reaction at the 2-position was achieved with aryl iodides with K3PO4 as base and SPhos ligand with Pd(OAc)2 (1-5 mol-%). A selective hydroarylation reaction (formal conjugate addition) was developed by using the same aryl iodides, benzyldiethylamine, Pd(OAc)2, and P(o-tol)3. The products were converted, either directly or after alkene reduction, through a Baeyer-Villiger oxidation into chiral 3- and 4-substituted 5-(hydroxymethyl)dihydrofuran-2(3H)-ones. Three new cross-coupling approaches to the derivatization of levoglucosenone are described and the products converted into butyrolactones.
AB - The chiral pool material (-)-levoglucosenone (6,8-dioxabicyclo[3.2.1]oct-2-en-4-one, LGO) has been substituted by using a series of Pd-mediated cross-coupling reactions. Iodination of LGO followed by Suzuki-Miyaura cross-coupling reaction with boronic acids by employing the Buchwald ligand SPhos with Pd(OAc)2 afforded 3-aryl derivatives in excellent yields. Selective Heck arylation reaction at the 2-position was achieved with aryl iodides with K3PO4 as base and SPhos ligand with Pd(OAc)2 (1-5 mol-%). A selective hydroarylation reaction (formal conjugate addition) was developed by using the same aryl iodides, benzyldiethylamine, Pd(OAc)2, and P(o-tol)3. The products were converted, either directly or after alkene reduction, through a Baeyer-Villiger oxidation into chiral 3- and 4-substituted 5-(hydroxymethyl)dihydrofuran-2(3H)-ones. Three new cross-coupling approaches to the derivatization of levoglucosenone are described and the products converted into butyrolactones.
KW - Chiral pool
KW - Cross-coupling
KW - Homogeneous catalysis
KW - Lactones
KW - Levoglucosenone
UR - http://www.scopus.com/inward/record.url?scp=84946224835&partnerID=8YFLogxK
U2 - 10.1002/ejoc.201501083
DO - 10.1002/ejoc.201501083
M3 - Article
AN - SCOPUS:84946224835
VL - 2015
SP - 6999
EP - 7008
JO - European Journal of Organic Chemistry
JF - European Journal of Organic Chemistry
SN - 1434-193X
IS - 32
ER -