Organocatalyzed Diels-Alder Reactions: Unexplored Hydrogen Bond Donor Catalysts

被引：0
作者：
Tiekink, Eveline H. [1 ]
Verdijk, Ron [1 ]
Hamlin, Trevor A. [1 ]
Bickelhaupt, F. Matthias [1 ,2 ,3 ]
机构：
[1] Vrije Univ Amsterdam, Dept Chem & Pharmaceut Sci, AIMMS, Boelelaan 1108, NL-1081 HZ Amsterdam, Netherlands
[2] Radboud Univ Nijmegen, Inst Mol & Mat, Heyendaalseweg 135, NL-6525 AJ Nijmegen, Netherlands
[3] Univ Johannesburg, Dept Chem Sci, Auckland Pk, ZA-2006 Johannesburg, South Africa
来源：
CHEMPLUSCHEM | 2025年
基金：
荷兰研究理事会;
关键词：
Activation strain model; Density functional calculations; Diels-Alder reactions; Activation strain analysis; Organocatalysis; CORRELATION-ENERGY; 2ND DERIVATIVES; METAL-FREE; DENSITY; APPROXIMATION; SELECTIVITY; ELEMENTS; SYSTEMS;
D O I：
10.1002/cplu.202500081
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
We have quantum chemically investigated the catalytic effect of hydrogen bonding organocatalysts, (H2N)(2)C=X (X=O, S, Se, NH, PH, AsH, CH2, SiH2 GeH2), such as urea, on the classic Diels-Alder reaction. All studied hydrogen bond donor catalysts enhance the Diels-Alder reaction between acrolein and 1,3-butadiene to a similar extent. Our activation strain and Kohn-Sham molecular orbital analyses show that these organocatalysts lower the reaction barrier by polarizing the pi-orbitals away from the reactive carbon atoms of acrolein, reducing the Pauli repulsion between the reactants. Interestingly, this catalytic mechanism is not limited to >C=X moieties with relatively electronegative X (e. g., O, S, NH) but extends to situations like >C=CH2 and even >C=SiH2.
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页数：8
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