TY - JOUR
T1 - Direct Catalytic Asymmetric Mannich-type Reaction of α,β-Unsaturated γ-Butyrolactam with Ketimines
AU - Lin, Shaoquan
AU - Kumagai, Naoya
AU - Shibasaki, Masakatsu
N1 - Funding Information:
This work was financially supported by JST, ACT-C, and KAKENHI (No. 25713002) from JSPS. We thank Dr. Tomoyuki Kimura for assistance in X-ray crystallography.
Publisher Copyright:
© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
PY - 2016/3/1
Y1 - 2016/3/1
N2 - We report a direct catalytic asymmetric Mannich-type addition of α,β-unsaturated γ-butyrolactam to α-ethoxycarbonyl ketimines promoted by a soft Lewis acid/Brønsted base cooperative catalyst. A thiophosphinoyl group on the nitrogen of ketimines was crucial for both electrophilic activation and α-addition of γ-butyrolactams. The obtained aza-Morita-Baylis-Hillman-type products bear an α-amino acid architecture with a tetra-substituted stereogenic center. Ambident nucleophile! A direct catalytic asymmetric Mannich-type addition of α,β-unsaturated γ-butyrolactam to α-ethoxycarbonyl ketimines promoted by a soft Lewis acid/Brønsted base cooperative catalyst has been developed (see scheme; Ph-BPE=1,2-bis(2,5-dimethylphospholano)ethane). The obtained aza-Morita-Baylis-Hillman-type products bear an α-amino acid architecture with a tetra-substituted stereogenic center.
AB - We report a direct catalytic asymmetric Mannich-type addition of α,β-unsaturated γ-butyrolactam to α-ethoxycarbonyl ketimines promoted by a soft Lewis acid/Brønsted base cooperative catalyst. A thiophosphinoyl group on the nitrogen of ketimines was crucial for both electrophilic activation and α-addition of γ-butyrolactams. The obtained aza-Morita-Baylis-Hillman-type products bear an α-amino acid architecture with a tetra-substituted stereogenic center. Ambident nucleophile! A direct catalytic asymmetric Mannich-type addition of α,β-unsaturated γ-butyrolactam to α-ethoxycarbonyl ketimines promoted by a soft Lewis acid/Brønsted base cooperative catalyst has been developed (see scheme; Ph-BPE=1,2-bis(2,5-dimethylphospholano)ethane). The obtained aza-Morita-Baylis-Hillman-type products bear an α-amino acid architecture with a tetra-substituted stereogenic center.
KW - amino acids
KW - asymmetric catalysis
KW - cooperative effects
KW - ketimines
KW - lactams
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U2 - 10.1002/chem.201600034
DO - 10.1002/chem.201600034
M3 - Article
AN - SCOPUS:84959441544
SN - 0947-6539
VL - 22
SP - 3296
EP - 3299
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
IS - 10
ER -