Enthalpy of the Diels-Alder reaction of cyclopentadiene and maleic anhydride

Breslauer, Kenneth J.; Kabakoff, David S.

doi:10.1021/jo00919a034

Cited by 10 publications

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“…One of the archetypal DA cycloadditions is the reaction between maleic anhydride and cyclopentadiene (Scheme ). For this reaction, the effects of oriented EEFs have thoroughly been studied both from theoretical , and experimental points of view. Then, for comparison purposes, this reaction has been selected to check the FDB β performance and to introduce the 2D representation of the chemical barriers for the kinetic product of the reaction.…”

Section: Resultsmentioning

confidence: 99%

Fast and Simple Evaluation of the Catalysis and Selectivity Induced by External Electric Fields

et al. 2021

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In the oriented external electric-field-driven catalysis, the reaction rates and the selectivity of chemical reactions can be tuned at will. The activation barriers of chemical reactions within external electric fields of several strengths and directions can be computationally modeled. However, the calculation of all of the required field-dependent transition states and reactants is computationally demanding, especially for large systems. Herein, we present a method based on the Taylor expansion of the field-dependent energy of the reactants and transition states in terms of their field-free dipole moments and electrical (hyper)polarizabilities. This approach, called field-dependent energy barrier (FDB β ), allows systematic onedimensional (1D), two-dimensional (2D), and three-dimensional (3D) representations of the activation energy barriers for any strength and direction of the external electric field. The calculation of the field-dependent FDB β energy barriers has a computational cost several orders of magnitude lower than the explicit electric field optimizations, and the errors of the FDB β barriers are within the range of only 1−2 kcal•mol −1 . The achieved accuracy is sufficient for a fast-screening tool to study and predict potential electric-fieldinduced catalysis, regioselectivity, and stereoselectivity. As illustrative examples, four cycloadditions (1,3-dipolar and Diels−Alder) are studied.

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Section: Resultsmentioning

confidence: 99%

Fast and Simple Evaluation of the Catalysis and Selectivity Induced by External Electric Fields

et al. 2021

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The Retro–Diels–Alder Reaction PartI.CCDienophiles

Rickborn

1998

Organic Reactions

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The Diels–Alder (“DA”) reaction is so familiar to organic chemists that the retro‐Diels–Alder or retro‐diene reaction (hereafter “rDA”) requires no conceptual introduction. However, a working definition is needed to indicate the coverage of this review. The intent is to include all reported examples of the general skeletal process excluded in this chapter. Any of the atoms in the starting material (cycloadduct) may be carbon or heteroatom, and substituents on all positions are allowed. In addition, any bond order available to the element in any oxidation state is included, as well as bonding to non‐nearest neighbor atoms (bicyclics, etc.). The volume of literature required separation of this review into two parts. Part I covers all expelled C–C dienophiles, i.e. those reactions that generate a new carbon‐carbon double or triple bond in the dienophile that is formed. Part II, to appear later, covers those expelled dienophiles in which one or both atoms is a heteroatom. Certain specific topics are intentionally omitted. These are: rDA reactions invoked under mass spectral conditions; rDA reactions of polymeric substrates; Electrocyclic processes, some of which are arguably very similar to rDA reactions (these are not addressed unless needed for clarification of an rDA sequence); and a thorough discussion of homo‐rDA reactions. CAS‐Online searches resulted in ca. 1,300 references, of which ca. 900 proved pertinent to the rDA topic as defined and delimited above. Active literature searching was halted in April 1995, but occasional more recent articles are included. Over 2,500 pertinent references were eventually found. Most were obtained by perusal of primary literature (articles) and secondary sources (books and reviews). Computer based search success was limited mainly by the failure of authors or abstractors to key‐word this topic, an especially common occurrence when the expelled dienophile was a simple substance such as N 2 or CO 2 . Overall, approximately 3,500 books, chapters, reviews, articles, and abstracts were consulted in an effort to make this review as comprehensive as possible. This was done with the certainty that some pertinent literature would be missed, tempered by the view that these omissions are probably also lost to any future rational search method. Many secondary sources proved valuable not only for in‐depth discussion of certain rDA reaction types, but also for providing comparisons with related topics. To assist the reader, these secondary sources are referenced (alphabetically by first author within broad subject areas) with a title or brief note on the topic(s) addressed. The first group lists earlier reviews with primary focus on rDA reactions, followed by items of Historical/General Interest, reviews that deal with Experimental Methods, DA reactions (general and specific), reviews of Related Topics (these impinge in more or less significant ways on rDA reactions), and general treatments of Theory and Mechanism.

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