TY - JOUR
T1 - Unprecedented Diastereoselective Arylogous Michael Addition of Unactivated Phthalides
AU - Sicignano, Marina
AU - Schettini, Rosaria
AU - Sica, Luisa
AU - Pierri, Giovanni
AU - De Riccardis, Francesco
AU - IZZO, Irene
AU - Maity, Bholanath
AU - Minenkov, Yury
AU - Cavallo, Luigi
AU - Della Sala, Giorgio
N1 - KAUST Repository Item: Exported on 2020-10-01
Acknowledgements: Financial support was provided from the University of Salerno (FARB). The computing resources used within this project have been provided by CRESCO/ENEAGRID High Performance Computing infrastructure and its staff. We thank Dr Patrizia Iannece for HR-ESI-MS
PY - 2019/4/8
Y1 - 2019/4/8
N2 - The first highly enantioselective arylogous Michael reaction (AMR) of 3-unsubstituted phthalides has been described. This phase-transfer methodology, which uses catalytic amounts of KOH/18-crown-6 catalyst in mesitylene in the presence of N,O-bis(trimethylsilyl)acetamide (BSA), gives access to a broad range of 3-monosubstituted phthalides with high levels of syn diastereoselectivity and good yields, starting from 3-unsubstituted derivatives and diverse α,β-unsaturated carbonyl compounds. The reaction also applies to unactivated 3-alkyl phthalides to afford 3,3-dialkyl derivatives. A plausible mechanism has been suggested. DFT analysis of possible transition states gives a rationale of the high syn diastereoselectivity observed and its correlation with the solvent's dielectric constant.
AB - The first highly enantioselective arylogous Michael reaction (AMR) of 3-unsubstituted phthalides has been described. This phase-transfer methodology, which uses catalytic amounts of KOH/18-crown-6 catalyst in mesitylene in the presence of N,O-bis(trimethylsilyl)acetamide (BSA), gives access to a broad range of 3-monosubstituted phthalides with high levels of syn diastereoselectivity and good yields, starting from 3-unsubstituted derivatives and diverse α,β-unsaturated carbonyl compounds. The reaction also applies to unactivated 3-alkyl phthalides to afford 3,3-dialkyl derivatives. A plausible mechanism has been suggested. DFT analysis of possible transition states gives a rationale of the high syn diastereoselectivity observed and its correlation with the solvent's dielectric constant.
UR - http://hdl.handle.net/10754/656080
UR - https://onlinelibrary.wiley.com/doi/abs/10.1002/chem.201900168
UR - http://www.scopus.com/inward/record.url?scp=85066920395&partnerID=8YFLogxK
U2 - 10.1002/chem.201900168
DO - 10.1002/chem.201900168
M3 - Article
C2 - 30779872
VL - 25
SP - 7131
EP - 7141
JO - Chemistry – A European Journal
JF - Chemistry – A European Journal
SN - 0947-6539
IS - 29
ER -