Synthesis of ethanol-d

Pasto, Daniel J.; Meyer, Gilbert Richard

doi:10.1021/jo01267a077

Cited by 29 publications

(31 citation statements)

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“…The ring-opening process was indicated to occur, with apparently no activation energy barrier, from the 6 rr-electron, closed-shell, singlet states when there are at least two nitrogen atoms at the 2and 3-positions [SI. The results of a subsequent detailed theoretical study of the 2-and 3-azoylidenes 4 and 5 at the 6-31G" level provided interesting insights on the effects of aromatic and nonaromatic rr systems versus nonbonded-pair orbital occupancy interactions [9]. The results of the calculations correlated well with the known chemistry of the substituted derivatives of 4 and 5 reported in the literature [91.…”

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confidence: 64%

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Theoretical studies on the diazacyclopentadienylidenes: An analysis of aromatic versus nonaromatic systems and singlet versus triplet reactivity

Pasto

1992

Heteroatom Chemistry

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confidence: 64%

“…The following convention will be used to specify the system and the electronic states as done in our earlier publication [9]. The positions of the two nitrogen atoms in the ring will be indicated by two numbers followed by N .…”

Section: F;)mentioning

confidence: 99%

Theoretical studies on the diazacyclopentadienylidenes: An analysis of aromatic versus nonaromatic systems and singlet versus triplet reactivity

Pasto

1992

Heteroatom Chemistry

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“…A surprising result was obtained in the reaction of enantioenriched (S)-(+)-1,3-dimethylallene with 1,1-diphenylethene, which does not lead to detectable formation of [2+2] cycloadducts, 30 but does result in the racemization of 1,3-dimethylallene. These results have been interpreted as it is shown in Scheme 22, which involves the reversible formation of the two diradical intermediates 65 and 66.…”

Section: Dimerization and Intermolecular [2+2] Cycloadditions Of Allementioning

confidence: 99%

Exploiting [2+2] cycloaddition chemistry: achievements with allenes

2010

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The allene moiety represents an excellent partner for the [2+2] cycloaddition with alkenes and alkynes, affording the cyclobutane and cyclobutene skeletons in a single step. This strategy has been widely studied under thermal, photochemical and microwave induced conditions. More recently, the use of transition metal catalysis has been introduced as an alternative relying on the activation of the allenic component. On the other hand, the intramolecular version has attracted much attention as a strategy for the synthesis of polycyclic compounds in a regio-and stereoselective fashion. This critical review focuses on the most recently developed [2+2] cycloadditions on allenes along with remarkable early works accounting for the mechanism, the regio-and diastereoselectivity of the cycloadducts formed (103 references).

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“…Theoretical calculations carried out at the HF/4-31G level (for basis set consistency with the calculations carried out much earlier in the author's laboratories) on the isodesmic reaction shown in equation (5) have shown that when X and Y in structure 1 are a pair donor groups, the 1,1-disubstituted ethene may enjoy ground-state stabilization or suffer ground-state destabilization. 13 When both X and Y are a pair of acceptor and donor groups, or when both are acceptor groups, the 1,1-disubstituted ethene suffers significant ground-state destabilization. 13 For consideration in later discussions, selected results of that calculational study are summarized in Table 1.…”

Section: Introductionmentioning

confidence: 99%

“…13 When both X and Y are a pair of acceptor and donor groups, or when both are acceptor groups, the 1,1-disubstituted ethene suffers significant ground-state destabilization. 13 For consideration in later discussions, selected results of that calculational study are summarized in Table 1. It is important to note that the 1-cyano-1-hydroxy combination of functional groups results in significant ground-state destabilization.…”

Section: Introductionmentioning

confidence: 99%

Theoretical analysis of the energy barriers for the rotational isomerization of the allyl and the 1-cyano-, 1-hydroxy- and 1-cyano-1-hydroxyallyl radicals

Pasto

1997

J. Phys. Org. Chem.

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An ab initio computational study was carried out on the ground-and transition-state structures for the rotational isomerization of the allyl and the 1-cyano, 1-hydroxy-and 1-cyano-1-hydroxyallyl radical systems in an attempt to gain an understanding of the factors affecting the relative energy barriers for rotational isomerization. The results of ESR rate measurements have indicated that there exists the presence of an 'extra' lowering of the energy barrier for the rotational isomerization of the 1-cyano-1-hydroxylallyl radical relative to the sum of the lowerings of the energy barriers for the rotational isomerization of the 1-cyano-and 1-methoxylallyl radical compared with the energy barrier for the rotational isomerization of the allyl radical. The 'extra' lowering of the energy barrier for the rotational isomerization of the 1-cyano-1-hydroxyallyl radical has been attributed to captodative stabilization of the transition structure for rotational isomerization. Prior calculational studies in the author's and other laboratories have resulted in the suggestion that captodative substitution does not always lead to 'extra' stabilization to a radical center. Recent calculations in the author's laboratories and the results reported in the present paper strongly suggest that ground-state effects can be dominant in determining the rate of a radical-forming reaction. The present paper describes the results of theoretical calculations on the allyl and substituted allyl radical systems that indicate that ground-state effects appear to dominate the relative rates of the rotational isomerization of the substituted allyl radicals.

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Synthesis of ethanol-d

Cited by 29 publications

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Theoretical studies on the diazacyclopentadienylidenes: An analysis of aromatic versus nonaromatic systems and singlet versus triplet reactivity

Theoretical studies on the diazacyclopentadienylidenes: An analysis of aromatic versus nonaromatic systems and singlet versus triplet reactivity

Exploiting [2+2] cycloaddition chemistry: achievements with allenes

Theoretical analysis of the energy barriers for the rotational isomerization of the allyl and the 1-cyano-, 1-hydroxy- and 1-cyano-1-hydroxyallyl radicals

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