2004
DOI: 10.1021/om0343317
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High Stereoselectivity and Facial Selectivity in Diels−Alder Cycloadditions of Novel Captodative Olefins:  α-Alkoxyvinyl(ethoxy)carbene Chromium Complexes with Cyclopentadienes

Abstract: A study of reactivity and selectivity of the new Fischer carbene complexes (CO)5CrC[C(CHR‘)(OR)]OCH2CH3 (3, R‘ = H, R = CH2CH3; 4, R‘ = H, R = CH2CH2CH3; 5, R‘ = H, R = CH2CH2CH2CH3; 6, R‘ = CH3 (E and Z), R = CH2CH3) was carried out in Diels−Alder cycloadditions with cyclopentadiene (1) and 1,2,3,4,5-pentamethylcyclopentadiene (7). The cycloadditions between the α-alkoxyvinyl(ethoxy)carbene complexes 3, 4, and 5 with 1 were found to be highly stereoselective, favoring the endo adduct at a much higher level … Show more

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Cited by 19 publications
(4 citation statements)
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“…Recently, we have reported the Diels−Alder reaction of (α-alkoxyvinyl)ethoxycarbene complexes ( 8 ) with pentamethylcyclopentadiene ( 4 ), which gave only the anti - exo diastereoisomer . The exo selectivity was probably due to the strong repulsive interactions between the metal moiety and the methyl group of the diene at the endo transition state.…”
Section: Resultsmentioning
confidence: 99%
See 1 more Smart Citation
“…Recently, we have reported the Diels−Alder reaction of (α-alkoxyvinyl)ethoxycarbene complexes ( 8 ) with pentamethylcyclopentadiene ( 4 ), which gave only the anti - exo diastereoisomer . The exo selectivity was probably due to the strong repulsive interactions between the metal moiety and the methyl group of the diene at the endo transition state.…”
Section: Resultsmentioning
confidence: 99%
“…Recently, we reported the reactivity and selectivity in the reaction of (α-alkoxyvinyl)ethoxycarbene complexes with 1,2,3,4,5-pentamethyl-1,3-cyclopentadiene, which produced new alkoxy-chelated tetracarbonyl carbene complexes with a high anti / exo selectivity . This study has now been extended to the reaction of the (arylethynyl)ethoxycarbene complexes 1 − 3 in Diels−Alder cycloadditions.…”
Section: Introductionmentioning
confidence: 95%
“…To initiate the reactivity study, benzylidene aniline 2a [43] and Fischer carbene complex 1 were utilized as model reagents [57]. Four anhydrous solvents (toluene, benzene, methyl t-butyl ether (MTBE), and THF) were tested to avoid the hydrolysis of 2a (Table 1, entries 1-4).…”
Section: Resultsmentioning
confidence: 99%
“…FCCs containing group VI transition metals [29,31–33] are very versatile in cyclization and cycloaddition reactions with an α,β‐unsaturated system under different conditions, [29] resulting in carbocycles, [34–39] heterocycles [29,40–43] and a diversity of other compounds. Chromium carbene complexes have shown particularly suitable reactivity, compared to the greater stability of tungsten and the extreme reactivity of molybdenum complexes [44–47] .…”
Section: Introductionmentioning
confidence: 99%