A Telescoped Photo-/Organo-Catalyzed Cross Dehydrogenative Coupling (CDC) between Glycine Derivatives and Ketones to Afford Nonproteinogenic Amino Acids (NPAAs) Enabled by Heterogeneous Continuous Flow Catalysis

被引：1

作者：

Poletti, Lorenzo ^{[1
]}

Codeca, Nicola ^{[1
]}

Ragno, Daniele ^{[1
]}

De Risi, Carmela ^{[1
]}

Toldo, Sofia ^{[2
]}

Bortolini, Olga ^{[2
]}

Shao, Jiaye ^{[3
]}

An, Lan ^{[3
]}

Lee, Daniel ^{[3
]}

D'Agostino, Carmine ^{[3
,4
]}

Dambruoso, Paolo ^{[5
]}

Massi, Alessandro ^{[1
]}

Carmine, Graziano Di ^{[2
]}

机构：

[1] Univ Ferrara, Dept Chem Pharmaceut & Agr Sci, I-44121 Ferrara, Italy

[2] Univ Ferrara, Dept Environm & Prevent Sci, I-44121 Ferrara, Italy

[3] Univ Manchester, Dept Chem Engn, Manchester M13 9PL, England

[4] Alma Mater Studiorum Univ Bologna, Dept Civil Chem Environm & Mat Engn, I-40131 Bologna, Italy

[5] CNR, Inst Organ Synth & Photoreact, I-40129 Bologna, Italy

来源：

ACS SUSTAINABLE CHEMISTRY & ENGINEERING | 2024年 / 12卷 / 41期

关键词：

photocatalysis; organocatalysis; continuousflow; non-proteinogenic amino acids; carbon nitride; telescoped reaction; GRAPHITIC CARBON NITRIDE; PHASE PEPTIDE-SYNTHESIS; BATCH; ORGANOCATALYSIS; WATER;

D O I：

10.1021/acssuschemeng.4c05931

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

We present a new sustainable and efficient approach that consists of a telescoped CDC/Mannich reaction in continuous flow to access enantiopure carbonyl derivatives of masked non-proteinogenic mmino acids (NPAAs). The protocol consists of two reactions: the C-H activation of glycine analogues enabled by mesoporous graphitic carbon nitride (mpg-CN), followed by a Mannich reaction between alpha-enolizable ketones or aldehyde, activated by a supported proline-like organocatalyst (Si-Ley), and the imine formed in the first step. The protocol was designed embracing the principles of green chemistry (metal-free catalysis, the reuse of medium and catalysts to reduce the E-factor, and the use of air for oxidation). Furthermore, good results were obtained in terms of yield and enantioselectivity (Y = up to 91% and ee = up to 99%). Long-term stability experiments and reactivation studies were performed providing excellent results in terms of the durability of the system; furthermore; we were able to obtain 1.8 g of the desired product of the benchmark reaction (gram scale) after cumulative runs. Furthermore, NMR measurements were employed to shine light on the deactivation of the catalysts during the operative conditions.

引用

页码：15193 / 15202

页数：10