Stereospecificity of dienophile addition to cycloheptatrienes

Goldstein, M. J.; Gevirtz, A.H.

doi:10.1016/s0040-4039(00)71680-7

Cited by 19 publications

(3 citation statements)

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“…CHT is a compound that classically undergoes Diels-Alder reactions via its norcaradiene valence isomer 5, as shown below (Scheme 3) for its reaction with maleic anhydride, which was first studied in 1939 by Kohler et al [3], with the correct structure of the norcaradiene-derived product first being proposed by Alder and Jacobs in 1953 [4]. Full stereochemical analysis of the Diels-Alder reactions of CHT in general [5], and more specifically of its reaction with maleic anhydride was accomplished by Goldstein and Gevirtz, and Ishitobi et al, respectively [6].…”

Section: Introductionmentioning

confidence: 99%

Sequential ene, Diels–Alder reactions of AF4-yne with 1,3,5-cycloheptatriene

Zhai

Wheelus

Battiste

et al. 2008

Journal of Fluorine Chemistry

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Section: Introductionmentioning

confidence: 99%

Sequential ene, Diels–Alder reactions of AF4-yne with 1,3,5-cycloheptatriene

Zhai

Wheelus

Battiste

et al. 2008

Journal of Fluorine Chemistry

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“…When 1 and cinnamic acid were treated in o-dichlorobenzene, 15 was exclusively obtained: mp 245°; methyl ester mp 150-151°; nmr (CDC13) 6.05 (d, 3-H), 6.22 (d, 6-H), 6.3 (q, 5-H), 7.0 (t, 4-H); J3A = 10.5, ,6 = 12, ,e = 6 Hz. Condensation of 2 with cinnamic acid gave the adduct 14: mp 235; methyl ester mp 134-135°; nmr (CDCh) 6.0 (d, 3-H), 6.8 (dd, 4-H), 6.95 (sextet, 5-H); J3A = 10, JiA = 12, = 12, = 5, /6a,6e = 15 Hz. These assignments were confirmed by nmr of the adducts obtained from 1 and 2 with trans-a-d-cinnamic acid.…”

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confidence: 99%

Novel aspects of the Diels-Alder reaction with 1,4-and 1,2-diphenylbutadienes under thermal and Lewis acid catalyzed conditions

Jain¹,

Mukerjee²,

Anand³

1974

J. Am. Chem. Soc.

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Some Novel Aspects of the Diels-Alder Reaction with 1,4-and 1,2-Diphenylbutadienes under Thermal and Lewis Acid Catalyzed Conditions1 Sir:A great deal of attention has been paid by theoretical chemists to explain the experimental facts of regio-and stereoselectivity of the Diels-Alder reaction ever since the propounding of the empirical rules by Alder and Stein,2 and two of the recent and more successful such treatments are those of Herndon3 and Houk.4 It was reported earlier by us5 that in the addition of ß-nitrostyrenes to 1,4-diphenylbutadiene electron withdrawing substituents in the 4'-position of the dienophile introduce striking stereoselectivity and lead to the formation of only the phenyl endo adducts (4). The work presented now shows some novel aspects of the stereoselectivity introduced by the Lewis acids and the steric control exerted by the 2-phenyl moiety in the addition of 1,2-diphenylbutadiene to ß-nitrostyrene and cinnamic acid. These effects have been explained on the basis of the preferred geometry of the transition state. Any unified theoretical treatment will have to encompass these facts.The addition reaction of 1 and 3 in benzene at 0°in presence of 1 molar equiv of SnCl4 or A1C13 gave exclusively the nitro endo adduct 5, in contrast to the formation of equal proportions of both the phenyl endo (1) Communication No.

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“…is formed in at least 80 % yield [3J on direct irradiation (Hanau Q-81 lamp, Pyrex filter, 2 h) of an ethereal solution (100 mg/300 ml) of "monohomobarrelene" (5a) [A,,, (ether) = 257 nm (E = 2060; €280 nm = 800)] cooled to -20 O C .Apparently this (277 + 2 x) cycloaddition ( 5 ) + (8) is not detectably (NMR analysis) accompanied by (2x + 2s) addition ( 5 ) + ( 4 ) in spite of the stereoelectronically favorable 141 exo-arrangement of the three-membered ring151 to the substituted (excited) C=C double bond. Moreover, there was no indication that (6a) was formed, although this product would be the one most expected on triplet sensitization[61.…”

mentioning

confidence: 99%