Diels-Alder Syntheses with Heteroatomic Compounds.

Needleman, Saul B.; Kuo, M. C. Chang

doi:10.1021/cr60219a002

Cited by 93 publications

(18 citation statements)

References 79 publications

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“…This partial thermal reversibility is also consistent with the proposed mechanism. 6 The dimerisation described here is highly stereoselective, with only one pair of diastereoisomers (from a possible four pairs) being formed; this is also consistent with the proposed mechanism.…”

supporting

confidence: 87%

Facile dimerisation of 3-benzylideneindoline-2-thiones

Thompson¹,

Boyd²,

Denny³

1993

J. Chem. Soc., Perkin Trans. 1

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supporting

confidence: 87%

Facile dimerisation of 3-benzylideneindoline-2-thiones

Thompson¹,

Boyd²,

Denny³

1993

J. Chem. Soc., Perkin Trans. 1

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“…) The final step, leading to the heterotricyclic product 3, is analogous to a Diels-Alder reaction in which a heterodienophile, acetaldehyde, reacts with a heterodiene. 7 The facility of the formation of the compound isolated is perhaps surprising. The driving force may be its precipitation.…”

Section: Resultsmentioning

confidence: 99%

Reaction of diaminomaleonitrile with acetaldehyde

Thanassi¹

1975

J. Org. Chem.

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The above supports the intermediacy of a symmetrical intermediate of the type V whose cleavage could then be affected by the substitution pattern but whose formation would be only slightly affected by inductive and solvent effects, since no charge is developed. VilaVllb VIII where the positive oxygen was three atoms away from the CH2X group, the relative insensitivity of the reaction to varying inductive effects and the good linear correlation would not be unreasonable. However, it is unreasonable to expect that Vllb could possibly be the exclusive intermediate over the range of substituents used in this study and in light of the strongly supported intermediacy of the two possible acylcarbonyl oxides in Bailey's study.3 The two acylcarbonyl oxides, II and III, could only arise from two four-membered ring precursors which differ in addition orientation, as in Vila and Vllb. If varying proportions of Vila and Vllb were formed, depending on the substituent, it would be highly unlikely that a linear correlation would exist; instead, as one went to more electron-donating substituents, Vila would be favored, resulting in marked curvature up as one went to decreasing a* values, something that is not observed.The initial rate-determining formation of a symmetrical complex, or of a symmetrical three-membered ring of the type VIII, cannot be ruled out. However, the relative insensitivity of the rate of reaction to changing substituents and changing solvent polarity does tend to make it less likely that charge is developed in the transition state.

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“…Importantly, in the context of this paper, heteroatom Diels-Alder reactions are well known with, for example, dienophiles containing O, N, and S, and specifically the thiocarbonyl group (C¼S), being well documented. [65,66] The combination of RAFT polymerization and heteroatom Diels-Alder chemistry has been demonstrated to be a versatile method for the synthesis of complex polymer architectures. In this atom economical approach, an electron deficient dithioester is typically employed, first, as a polymerization mediating agent and subsequently, post-polymerization, as the reactive dienophile in the cycloaddition step.…”

Section: Reversible Addition-fragmentation Chain Transfer (Raft) and mentioning

confidence: 99%