Ab initio study of the Diels–Alder reactions of prop-2-enethial

Bachrach, Steven M.; Jiang, Sulin

doi:10.1039/a705343f

Cited by 4 publications

(6 citation statements)

References 30 publications

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“…On the other hand, the sum of the active bond orders for most of the reaction is very close to 7, the value one would associate with a concerted reaction. We have typically found a sum indicative of concert for hetero-Diels−Alder reactions. ,, The only outlier is reaction 5, and here the sum is off by only 0.25, not a large amount considering the extrapolations involved in the fitting procedure.…”

Section: Resultsmentioning

confidence: 81%

“…While all substituents lengthen this bond, the longest are for the methoxy compounds P5x and P5n , though the Se−C 2 distance in the dicyano compound is almost as long. The methoxy substituent result suggests perhaps an anomeric effect, but the C−O distances do not reflect this, and the variation in the Se−C 2 length is much less than what is seen on the pyrans or thiopyrans . Since all of the substituents lead to longer bonds, it is easiest to rationalize the effect as simply due to steric interactions.…”

Section: Resultsmentioning

confidence: 98%

“…We have long been interested in pericyclic reactions of heterosystems. − In this paper, we report a theoretical examination of the Diels−Alder reaction of a series of substituted CSe systems. We find that substituent effects conform to the standard FMO model.…”

Section: Introductionmentioning

confidence: 99%

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Theoretical Study of the Diels−Alder Reaction of Selenoaldehydes and Selenoketones

Bachrach

Jiang

1999

J. Org. Chem.

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The Diels-Alder reaction of a series of substituted selenoaldehydes (Se=CHR; R = H, F, Me, OMe, CH(2)F, CF(3), and CN) or selenoketones (Se=CR(2); R = Me and CN) with 1,3-butadiene or 2-methoxy-1,3-butadiene to yield 3,6-dihydro-2H-selenopyrans were examined using B3LYP with a modified 6-31G basis set. This method is compared with results from a number of standard ab initio procedures and compares well with post-HF results. The Diels-Alder reaction of the selenocarbonyl compounds proceeds through a concerted, though asynchronous, transition state. Strong electron-withdrawing groups alter the mechanism; a charge-transfer complex is first formed, followed by a concerted TS before reaching the heterocyclic product. The transition state geometry, regiochemistry, and dependence of the activation barrier on substituents can be understood in terms of FMO theory.

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Section: Resultsmentioning

confidence: 81%

Section: Resultsmentioning

confidence: 98%

See 1 more Smart Citation

Theoretical Study of the Diels−Alder Reaction of Selenoaldehydes and Selenoketones

Bachrach

Jiang

1999

J. Org. Chem.

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“…The corresponding potential energy surfaces are very complex, having a large number of species that often present several possible conversion and fragmentation paths. This complexity is not surprising because it has also been encountered in a recent theoretical study of a related system, SC 5 …”

Section: Introductionmentioning

confidence: 87%

Theoretical Study of the SC₃H_m⁺Systems,m= {3, 4}

Gómez

Flores

2003

J. Phys. Chem. A

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A comprehensive theoretical study of the potential energy surfaces of the lowest-lying doublet and quartet electronic states of the SC 3 H 4 + system has been performed by means of a combination of density functional and ab intio methods. The potential energy surfaces corresponding to the lowest doublet and quartet electronic states have turned out to be extremely complex. Twenty-six doublet species and twenty-four quartet species have been identified, some of them having several stable conformations. The quartet states are normally much higher in energy than the doublet states. The absolute minimum is the methylthioketene cation, but the 2H-thiete cation, the thioacrolein cation, and the methylthiirene cation lie very close in energy; all of them are doublet states. The most stable quartet species is the thioxyallyl cation. In addition, a rather detailed analysis of the fragmentation of this system has been made. All of the products that are obtained in the S + + CH 3 CCH reaction, which is an important step in the generation of sulfur-containing cumulenes of astrophysical significance, have been included in this analysis, namely, a number of states of the SC 3 H 3 + , HCS + , C 3 H 3 + , C 2 H 3 , and C 3 H 4 + systems. Special attention has been paid to the SC 3 H 3 + system. In addition, the interaction between S + and CH 3 CCH through a number of electronic states has been studied by means of a multireference configuration interaction approach. The results suggest that an intersystem crossing process leading to the doublet potential energy surface of the SC 3 H 4 + system may play a key role. Some potentially crucial reaction mechanisms have been proposed.

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“…Likewise, substantial attention has been paid to hetero-DA processes for the synthesis of six-membered heterocycles . Azadienes have been by far the most frequently used synthons for this purpose; however, a number of DA processes with thiadienes have also been reported …”

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confidence: 99%

Novel [4 + 2] Cycloaddition between Thiobenzophenone and Aryl-Substituted Alkenes via Photoinduced Electron Transfer

2007

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Ab initio study of the Diels–Alder reactions of prop-2-enethial

Cited by 4 publications

References 30 publications

Theoretical Study of the Diels−Alder Reaction of Selenoaldehydes and Selenoketones

Theoretical Study of the Diels−Alder Reaction of Selenoaldehydes and Selenoketones

Theoretical Study of the SC₃H_m⁺Systems,m= {3, 4}

Novel [4 + 2] Cycloaddition between Thiobenzophenone and Aryl-Substituted Alkenes via Photoinduced Electron Transfer

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Ab initio study of the Diels–Alder reactions of prop-2-enethial

Cited by 4 publications

References 30 publications

Theoretical Study of the Diels−Alder Reaction of Selenoaldehydes and Selenoketones

Theoretical Study of the Diels−Alder Reaction of Selenoaldehydes and Selenoketones

Theoretical Study of the SC3Hm+Systems,m= {3, 4}

Novel [4 + 2] Cycloaddition between Thiobenzophenone and Aryl-Substituted Alkenes via Photoinduced Electron Transfer

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Theoretical Study of the SC₃H_m⁺Systems,m= {3, 4}