9‐Stannafluorenes: 1,4‐Dimetal Equivalents for Aromatic Annulation by Double Cross‐Coupling

Nagao, Ikuhiro; Shimizu, Masaki; Hiyama, Tamejiro

doi:10.1002/anie.200903779

Cited by 107 publications

(62 citation statements)

References 42 publications

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“…1 H NMR (500 MHz, CDCl 3 ): δ =7.52–7.56 (m, 4 H, C5‐H, C6‐H, C9‐H, C10‐H), 8.06 (s, 2 H, C3‐H, C1‐H), 8.21–8.24 (m, 2 H, C4‐H, C11‐H), 8.41–8.45 (m, 2 H, C7‐H, C8‐H); 13 C NMR (126 MHz, CDCl 3 ): δ =117.2 (d, C3, C1), 123.7 (d, C7, C8), 124.4 (d, C4, C11), 127.1 (d, C6, C9), 127.6 (d, C5, C10), 128.4 (s, C3b, C11a), 129.6 (s, C7a, C7b), 135.4 (s, C3a, C11b). The spectroscopic data are in agreement with those reported in the literature 7…”

Section: Methodssupporting

confidence: 91%

“…A second procedure, which also delivered unsatisfactory yields, was based on the reaction of 9‐bromomethyl‐10‐chloromethylphenanthrene with sodium sulphide 6. More recently, a higher yielding process was introduced by Hiyama et al7 making use of 9‐stannafluorenes as benzannulation precursor to be connected with the respective ortho ‐substituted dihaloarenes or dihalohetarenes. With 3,4‐dibromothiophene as dielectrophile the tin reagent gave the desired product in high yield employing Pd(P t Bu 3 ) 2 as the catalyst.…”

Section: Introductionmentioning

confidence: 99%

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Modular Synthesis of Phenanthro[9,10‐c]thiophenes by a Sequence of CH Activation, Suzuki Cross‐Coupling and Photocyclization Reactions

Schnapperelle

Bach

2014

Chemistry A European J

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A total number of 15 different 3,4-diarylthiophenes were synthesized, which bear a chlorine atom in ortho-position of one of the aryl substituents. One aryl group was introduced by an oxidative cross-coupling reaction, involving a CH activation at C4(3) of the thiophene core. The other aryl group was in most cases introduced by a Suzuki cross-coupling reaction, which succeeded the oxidative cross-coupling step. Photocyclization reactions of the 3,4-diarylthiophenes were performed in a solvent mixture of benzene and acetonitrile (50:50 v/v) at λ=254 nm and proceeded to the title compounds in yields of 60-82 %. The selectivity of the photocyclization was determined at the ortho-chloro-substituted aryl ring by the position of the chlorine substituent. At the other ring, a single regioisomer was observed for phenyl and para-substituted phenyl groups. For 2-naphthyl and ortho-substituted phenyl rings a clear preference was observed in favor of a major regioisomer, while meta-substitution in the phenyl ring led to a about 1:1 mixture of 5- and 7-substituted phenanthro[9,10-c]thiophenes. Mechanistically, the photocyclization is likely to occur as a photochemically allowed, conrotatory [(4n+2)π] process accompanied by elimination of HCl. It was shown for two phenanthro[9,10-c]thiophene products that they can be readily brominated in positions C1 and C3 (74-77 %), which in turn allows for further functionalization at these positions, for example, in the course of halogen-metal exchange and polymerization reactions.

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Section: Methodssupporting

confidence: 91%

Section: Introductionmentioning

confidence: 99%

Modular Synthesis of Phenanthro[9,10‐c]thiophenes by a Sequence of CH Activation, Suzuki Cross‐Coupling and Photocyclization Reactions

Schnapperelle

Bach

2014

Chemistry A European J

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“…113 Using this approach Tilley et al prepared a number of structurally related Si, S, P, Ge and Sn-containing heterofluorenes and studied their optoelectronic properties in detail. 114 Of note for this current review, the stannafluorenes 119,120 Each compound was characterized by X-ray crystallography however no further comparative study on their optoelectronic properties has been reported to date. The Ohshita group has extensively explored bithiophenes as active components of conjugated materials, and in 2013 they prepared 1,1-diphenyl-3,6bis(trimethylsilyl)dithienostannole (124) and di(benzo[b]thieno)-1,1-diphenylstannole (125) (Fig.…”

Section: Tinmentioning

confidence: 99%

Marriage of heavy main group elements with π-conjugated materials for optoelectronic applications

2016

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This review article summarizes recent progress in the synthesis and optoelectronic properties of conjugated materials containing heavy main group elements from Group 13-16 as integral components. As will be discussed, the introduction of these elements can promote novel phosphorescent behavior and support desirable molecular and polymeric properties such as low optical band gaps and high charge mobilities for photovoltaic and thin film transistor applications.

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“…To overcome this problem, they prepared the more complicated desymmetrized chlorodiarylthiophene 3 and successfully converted it to phenanthrothiophene 1 by irradiation with 254‐nm light. Other approaches that have been used to make phenanthro[9,10‐ c ]thiophene and derivatives include Hindsburg condensation of a diester sulfide with phenanthroquinone; ring closure using sodium sulfide and a phenanthryl dihalide or tetrahalide; and Stille coupling of a 9‐stannafluorene with a dibromothiophene . To develop a more efficient and versatile synthesis for substituted phenanthrenes, we decided to reexamine the simple cyclo‐oxidation of diarylthiophenes.…”

Section: Figurementioning

confidence: 99%

Synthesis of Phenanthro[9,10‐c]thiophenes by 2,3‐Dichloro‐5,6‐dicyano‐1,4‐benzoquinone (DDQ)‐Promoted Cyclo‐Oxidation

2019

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A new method to prepare phenanthro[9,10‐c]thiophenes has been developed. In the presence of triflic acid, 3,4‐diaryl thiophenes undergo 2,3‐dichloro‐5,6‐dicyano‐1,4‐benzoquinone (DDQ)‐promoted cyclo‐oxidation. NMR and computational studies indicate that protonation of the thiophene plays a key role in this reaction. The reaction can be used to prepare phenanthro[9,10‐c]thiophene, as well as derivatives with alkyl, bromo, and methoxy substituents. However, the yields and selectivity of the reaction depend on both the nature and location of the substituents. Bis(3‐methoxyphenyl)thiophene reacts under these conditions to give the desired product in 57 % yield, while bis(4‐methoxyphenyl)thiophene gives no product. Bis(3‐bromophenyl)thiophene did not react, but cyclo‐oxidation of bis(4‐bromophenyl)thiophene provides the desired product in 34 % yield.

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9‐Stannafluorenes: 1,4‐Dimetal Equivalents for Aromatic Annulation by Double Cross‐Coupling

Cited by 107 publications

References 42 publications

Modular Synthesis of Phenanthro[9,10‐c]thiophenes by a Sequence of CH Activation, Suzuki Cross‐Coupling and Photocyclization Reactions

Modular Synthesis of Phenanthro[9,10‐c]thiophenes by a Sequence of CH Activation, Suzuki Cross‐Coupling and Photocyclization Reactions

Marriage of heavy main group elements with π-conjugated materials for optoelectronic applications

Synthesis of Phenanthro[9,10‐c]thiophenes by 2,3‐Dichloro‐5,6‐dicyano‐1,4‐benzoquinone (DDQ)‐Promoted Cyclo‐Oxidation

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