A New Palladium-Catalyzed Benzannulation of Conjugated Enynes

Saito, Shinichi; Salter, Matthew M.; Gevorgyan, Vladimir; Tsuboya, Norie; Tando, Kazushi; Yamamoto, Yoshinori

doi:10.1021/ja9600486

Cited by 121 publications

(51 citation statements)

References 9 publications

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“…[22] Yamamoto et al reported palladium-catalyzed macrocyclizations to form exomethylene paracyclophanes based on intramolecular benzannulation of conjugated enynes. [23] Wullf et al reported benzannulation reactions of Fischer carbene complexes with alkynes to form meta-and paracyclophanes. [24] Shinokubo and Oshima et al reported [RhCl(PPh 3 ) 3 ]-catalyzed macrocyclizations to form ortho-and metacyclophanes by intramolecular [2+2+2] cycloaddition of triynes in an aqueous/ organic biphasic system.…”

Section: Entry 4)mentioning

confidence: 99%

Chemo‐ and Regioselective Intermolecular Cyclotrimerization of Terminal Alkynes Catalyzed by Cationic Rhodium(I)/Modified BINAP Complexes: Application to One‐Step Synthesis of Paracyclophanes

Tanaka

Toyoda

Wada

et al. 2005

Chemistry A European J

145

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A highly regioselective intermolecular cyclotrimerization of terminal alkynes has been developed based on the use of the cationic rhodium(I)/DTBM-Segphos complex. This method can be applied to a variety of terminal alkynes to provide 1,2,4-trisubstituted benzenes in high yield and with high regioselectivity. A chemo- and regioselective intermolecular crossed-cyclotrimerization of dialkyl acetylenedicarboxylates with a variety of terminal alkynes has also been developed based on the use of the cationic rhodium(I)/H8-BINAP complex, furnishing 3,6-disubstituted phthalates in high yields. It constitutes a highly efficient new method for intermolecular crossed-cyclotrimerization of two different monoynes in terms of catalytic activity, chemo- and regioselectivity, scope of substrates, and ease of operation. The versatility of this new crossed-alkyne cyclotrimerization procedure is demonstrated through its application to one-step synthesis of a [6]metacyclophane and [7]-[12]paracyclophanes from the corresponding terminal alpha,omega-diynes. Mechanistic studies have revealed that the chemo- and regioselectivity of this crossed-alkyne cyclotrimerization are determined by the preferential formation of a specific rhodium metallacycle derived from a terminal alkyne and a dialkyl acetylenedicarboxylate.

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Section: Entry 4)mentioning

confidence: 99%

Chemo‐ and Regioselective Intermolecular Cyclotrimerization of Terminal Alkynes Catalyzed by Cationic Rhodium(I)/Modified BINAP Complexes: Application to One‐Step Synthesis of Paracyclophanes

Tanaka

Toyoda

Wada

et al. 2005

Chemistry A European J

145

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“…For example, cyclophanes were prepared by the intramolecular cyclization of bisenynes (Chart 3). [10][11][12][13] The reactivity of ethoxycarbonylenynes was much higher compared to alkylenynes, and some cyclodimerization reactions proceeded at rt (Table 2). (Z)-Enynes were generally more reactive compared to (E)-enynes ( Table 2, entries 1-2).…”

Section: -7)mentioning

confidence: 99%

Development of New Cycloaddition Reactions Based on the Unique Reactivity of Unsaturated Hydrocarbons

Saito

2005

CHEMICAL & PHARMACEUTICAL BULLETIN

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We discovered that the reactivity of some conjugated and electron-deficient hydrocarbons was quite different in the presence of transition metal catalysts. In this review we report our development and applications of the highly selective palladium and nickel-catalyzed cycloaddition reactions of unsaturated hydrocarbons such as conjugated enynes, electron-deficient allenes, and electron-deficient methylenecyclopropanes. Some homocoupling reactions as well as co-cyclization reactions were described. The efficient synthesis of 4-7 membered carbocycles was achieved.

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“…[4] Moreover, alkyne activation by other complexes forms 1-metallacyclopentadiene, which incorporates with another alkyne molecule or undergoes dimerization to yield benzene derivatives C [5] and cyclooctatetraenes D, [6,7] respectively. Unsubstituted C and D (R 1 = R 2 = H) generated from ethyne were first observed by Reppe et al [8] Since then, these reactions have been studied intensively.…”

Section: Introductionmentioning

confidence: 99%

Palladium‐Catalyzed Cycloisomerizations of Diarylacetylenes: Synthesis, Structures, and Physical Properties of Highly Substituted Naphthalenes and 8,8 a‐Dihydrocyclopenta[a]indenes

Tai

Tiao

et al. 2011

Chemistry A European J

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Depending on the electronic properties of their substituents, the major products generated by palladium-catalyzed cycloisomerizations of diarylalkynes are either highly substituted 8,8a-dihydrocyclopenta[a]indenes 3 or naphthalenes 4. The structures of these compounds were verified by X-ray crystallographic analysis. Many functional groups tolerated the reaction conditions evaluated in this study. The isotope-labeled experiments indicated that added water has a critical role in forming both classes of compounds. The photophysical and electrochemical properties of cycloadducts 3 and their analogues were systematically studied and compared with computational predictions based on density functional theory. Dihydrocyclopenta[a]indenes 3 in either solid or liquid form display strong luminescence, whereas cyclopenta[a]indene 11 j is practically nonfluorescent. The functional groups directly attached to the backbone of compound 3 significantly influenced physical properties. The steric effect arising from the aryl substituents caused different luminescence phenomena, including aggregation-induced and -enhanced emission.

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A New Palladium-Catalyzed Benzannulation of Conjugated Enynes

Cited by 121 publications

References 9 publications

Chemo‐ and Regioselective Intermolecular Cyclotrimerization of Terminal Alkynes Catalyzed by Cationic Rhodium(I)/Modified BINAP Complexes: Application to One‐Step Synthesis of Paracyclophanes

Chemo‐ and Regioselective Intermolecular Cyclotrimerization of Terminal Alkynes Catalyzed by Cationic Rhodium(I)/Modified BINAP Complexes: Application to One‐Step Synthesis of Paracyclophanes

Development of New Cycloaddition Reactions Based on the Unique Reactivity of Unsaturated Hydrocarbons

Palladium‐Catalyzed Cycloisomerizations of Diarylacetylenes: Synthesis, Structures, and Physical Properties of Highly Substituted Naphthalenes and 8,8 a‐Dihydrocyclopenta[a]indenes

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