1970
DOI: 10.1021/jo00829a065
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Photochemical and thermal 1,2- and 1,4-cycloaddition reactions of azodicarbonyl compounds with monoolefins

Abstract: Dialkyl azodiformates form dihydrooxadiazines with indene, dihydro-1,4-dioxine, vinylene carbonate, cisand irons-1,2-dimethoxyethylene, and vinyl acetate by 1,4 addition; 1,2 addition yielding diazetidines is observed with vinyl ethers. Diazetidines also result from the addition of 4-phenyl-A'-1,2,4-triazoline-3,5-dione (PTD) to indene and dihydro-1,4-dioxine. Dihydrooxadiazines are formed in a concerted Diels-Alder reaction with inverse electron demand, the diazetidines via dipolar intermediates. The accelera… Show more

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Cited by 87 publications
(27 citation statements)
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“…83 Herein, the application of the cycloaddition chemistry to the synthesis of 2-amino-2-deoxyglycosides is discussed. [84][85][86][87][88][89] Based on the published mechanistic studies of this reaction with simple substrates, Leblanc and co-workers reasoned that the diastereoselectivity of the cycloadducts would be most readily attainable with a rigid substrate having an appropriately placed substituent-for example, allylsubstituted cyclic vinyl ethers. 90 Since glycals fit this criterion, Leblanc et al explored the possibility of applying this reaction to the synthesis of 2-aminosugars from glycals.…”
Section: Cycloaddition Reactionsmentioning
confidence: 99%
“…83 Herein, the application of the cycloaddition chemistry to the synthesis of 2-amino-2-deoxyglycosides is discussed. [84][85][86][87][88][89] Based on the published mechanistic studies of this reaction with simple substrates, Leblanc and co-workers reasoned that the diastereoselectivity of the cycloadducts would be most readily attainable with a rigid substrate having an appropriately placed substituent-for example, allylsubstituted cyclic vinyl ethers. 90 Since glycals fit this criterion, Leblanc et al explored the possibility of applying this reaction to the synthesis of 2-aminosugars from glycals.…”
Section: Cycloaddition Reactionsmentioning
confidence: 99%
“…The slightly inverse KIE (k H /k D = 0.98 ± 0.02) clearly rules out the possibility that allylic hydrogen abstraction occurs in a slow step, compared to the preceding transition state of AI formation. If we consider formation of AI in the rate-limiting step, significant inverse a-and b-secondary KIEs would be expected 19 essentially due to the rehybridization of the olefinic carbons from sp 2 to sp 3 . It seems that in the addition of PTAD to 61-d 0 , the transition states of the two reaction steps are close in energy, with formation of AI probably being slightly higher.…”
Section: Diastereoselectivitymentioning
confidence: 99%
“…20 In that study we explored the diastereoselectivity of the ene reaction of MTAD with allylic alcohol 63-d 0 . For this reason, we also used its deuterated analogs 63-d 9 , 63Z-d 3 , and 63E-d 3 (Scheme 14).…”
Section: Figurementioning
confidence: 99%
“…Among these, the formation of a closed, three-membered aziridinium imide (AI) intermediate ( Figure 1) was the most popular, and initially found support in the results of trapping experiments. [11,12] Subsequently, isotope effect measurements on deuterium-labeled tetramethylethylenes (TMEs) [3,4] and 2-butenes [5,6] also suggested the formation of an AI intermediate in the rate-determining step of the reaction. Thus, large intramolecular kinetic isotope effects (KIEs) were found in the ene reactions of RTADs with the cis-related methyl and deuteriomethyl groups in substrates 1 and 2 (H/D isotopic competition; Scheme 1), whereas only a small isotope effect was observed with the trans-related groups in compound 3 (no isotopic competition).…”
Section: Introductionmentioning
confidence: 99%