The Hayashi Rearrangement of Substituted o-Benzoylbenzoic Acids

Sandin, Reuben B.; Melby, Russell; Crawford, Robert J.; McGreer, Donald E.

doi:10.1021/ja01596a069

Cited by 13 publications

(4 citation statements)

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Section: Resultsmentioning

confidence: 99%

“…[24,26,27] These species govern the interactions between the different positively charged fleeting organic intermediates encountered during the reversible Hayashi equilibrium rearrangement and, therefore, their relative stability. [31][32][33] Inspired by the representation of Cristol, [22b] a rational mechanism can be drawn (Scheme 3) that involves spirocyclic cation 35 as a common key intermediate during the Hayashi rearrangement. A rationalization of the selectivity observed for 9 might be explained by a comparison of the relative stabilities of fleeting intermediates 32 and 38 and/ Scheme 3.…”

Section: Resultsmentioning

confidence: 99%

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Highly Selective Three‐Step Synthesis of Rhein in Chloroaluminate Molten Salt: Preclusion of the Hayashi Rearrangement

et al. 2009

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An expeditious, three‐step synthesis of rhein (2) was optimized starting from bis(N,N‐diethyl)‐5‐methoxybenzene‐1,3‐dicarboxamide. The key final step, involving deprotection/cyclization of ortho‐benzoylbenzoic acid 9 in acidic chloroaluminate molten salts, yielded the desired natural product with high selectivity and good overall yield by precluding the competitive Hayashi rearrangement.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Highly Selective Three‐Step Synthesis of Rhein in Chloroaluminate Molten Salt: Preclusion of the Hayashi Rearrangement

et al. 2009

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“…This rearrangement was found to occur on various substituted o-benzoyl [104,105] and o-aroylbenzoic acids [106] and it was one important step in the synthesis of benzophenanthridine alkaloid (AE )-chelidonine [107] and of an isoquinoline-5,10-dione based DNA intercalator. [108] A similar process was recently developed and made use of isothiocyanatobenzene derivatives (e.g., 26) for the AlCl 3 -catalyzed synthesis of benzothiazines (e.g., 27) in good yield as depicted in Scheme 34.…”

Section: Miscellaneousmentioning

confidence: 99%

The Aromatic Carbon–Carbon ipso‐Substitution Reaction

Bonesi

Fagnoni

2010

Chemistry A European J

129

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The aim of this review is to illustrate what we have dubbed an aromatic carbon-carbon ipso-substitution reaction in which a new Ar-C bond is formed at the expense of another Ar-C bond. The potentiality of several C-based leaving groups including alkyl, carbinol, CN, COOH, and carbonyl groups in arylation reactions will be illustrated accordingly for the preparation of biphenyl-, vinyl-, alkynyl-, and alkyl-substituted aromatics.

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“…The proposed mechanism for this reaction, shown in Scheme , involves the initial oxidative addition of substrate 1 to nickel(0) to form complex A . − Subsequent ipso -electrophilic attack of the leaving aryl group affords the seven-membered intermediate B . Ensuing elimination of the nitrile and coordination of alkyne 2 give the five-membered nickelacycle C .…”

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confidence: 99%