Synthesis of Biaryl Compounds through Three‐Component Assembly: Ambidentate Effect of the <i>tert</i>‐Butyldimethylsilyl Group for Regioselective Diels–Alder and Hiyama Coupling Reactions

Akai, Shuji; Ikawa, Takashi; Takayanagi, Sho‐ichi; Morikawa, Yuki; Mohri, Shinya; Tsubakiyama, Masaya; Egi, Masahiro; Wada, Y.; Kita, Yasuyuki

doi:10.1002/anie.200803011

Cited by 93 publications

(36 citation statements)

References 33 publications

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“…Benzyne, cyclohexyne, and cyclopropene derivatives react productively with 26 to give the expected Diels-Alder adducts (entries 4–6, Table 1). 29,30,31 Each of these structures comprises the pentacyclic framework of BTX. We have found dienophile generation to be most effective using CsF to promote elimination of a vicinally-substituted silyl-vinyl triflate or -vinyl halide, and reaction efficiency is excellent for two of the examples shown.…”

Section: Resultsmentioning

confidence: 99%

Modular synthesis of the pentacyclic core of batrachotoxin and select batrachotoxin analogue designs

Devlin

Bois

2013

Chem. Sci.

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Pentacyclic analogues of the potent voltage-gated sodium ion channel agonist batrachotoxin can be accessed through an intermediate furan by exploiting Diels-Alder cycloaddition reactions with ring-strained dienophiles. The use of 3-bromofuran as a 1,2-dianion equivalent, the application of carbamate reductive N-alkylation for homomorpholine ring assembly, and the demonstration of CsF as an effective reagent for generating benzyne, cyclohexyne, and related dienophiles underscore this work.

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Section: Resultsmentioning

confidence: 99%

Modular synthesis of the pentacyclic core of batrachotoxin and select batrachotoxin analogue designs

Devlin

Bois

2013

Chem. Sci.

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“…[20] In summary,w eh ave developed an iridium-catalyzed, peri-borylation of naphthalene derivatives and analogous polyaromatic hydrocarbons directed by ah ydrosilyl group under mild conditions with broad functional-group tolerance. [20] In summary,w eh ave developed an iridium-catalyzed, peri-borylation of naphthalene derivatives and analogous polyaromatic hydrocarbons directed by ah ydrosilyl group under mild conditions with broad functional-group tolerance.…”

Section: Angewandte Chemiementioning

confidence: 99%

Iridium‐Catalyzed, Silyl‐Directed, peri‐Borylation of C−H Bonds in Fused Polycyclic Arenes and Heteroarenes

Hartwig

2018

Angew Chem Int Ed

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peri-Disubstituted naphthalenes exhibit interesting physical properties and unique chemical reactivity, due to the parallel arrangement of the bonds to the two peri-disposed substituents. Regioselective installation of a functional group at the position peri to 1-substituted naphthalenes is challenging due to the steric interaction between the existing substituent and the position at which the second one would be installed. We report an iridium-catalyzed borylation of the C-H bond peri to a silyl group in naphthalenes and analogous polyaromatic hydrocarbons. The reaction occurs under mild conditions with wide functional group tolerance. The silyl group and the boryl group in the resulting products are precursors to a range of functional groups bound to the naphthalene ring through C-C, C-O, C-N, C-Br and C-Cl bonds.

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“…The synthetic protocol of Akai et al was used. 45 A solution of bromine (0.50 mL, 9.7 mmol) in dichloromethane (10 mL) was added dropwise to a solution of 2,4-di-tert-butylphenol in dichloromethane (2 mL) at 0°C. After stirring of the orange solution for an additional hour at this temperature, water was added and the phases were separated.…”

Section: Bis(tetrahydrofuran)sodium Almebate (3)mentioning

confidence: 99%

Synthesis and structure of salts of a sterically shielded, lipophilic, C2-symmetric, fluxional aluminate

Söhner¹,

Küppers²,

Wackerow³

et al. 2014

Arkivoc

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Multi-gram amounts of halogen-free lipophilic aluminate salts have been prepared, featuring two sterically demanding chelating ligands derived from a methane-2,2´-bisphenolate. The ligand is prepared by condensation of two equivalents of 2,4-di-tert-butylphenol with acetone induced by boron fluoride etherate. The C 2 -symmetry of this "almebate" anion implies helical chirality. Substantial steric shielding of the aluminate core results in high stability towards aqueous bases. Almebate salts hydrolyze in aqueous acetic acid at room temperature within days. Tetraphenylphosphonium and tetrabutylammonium salts have been prepared by salt metatheses. Sodium almebate can be activated thermally, generating electrophilic sodium(I) with a low coordination number. It eliminates chloride ligands from an N-heterocyclic carbene gold chloride complex, proven by a single-crystal X-ray diffraction study. The barrier of molecular racemization by a degenerate rearrangement of the intrinsically chiral almebate anion in acetone has been determined to be G ‡ 53.6 ± 2 kJ mol -1 from four 1 H NMR coalescence phenomena (500 MHz; 258 K, 273 K, 283 K, 290 K).

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Synthesis of Biaryl Compounds through Three‐Component Assembly: Ambidentate Effect of the tert‐Butyldimethylsilyl Group for Regioselective Diels–Alder and Hiyama Coupling Reactions

Cited by 93 publications

References 33 publications

Modular synthesis of the pentacyclic core of batrachotoxin and select batrachotoxin analogue designs

Modular synthesis of the pentacyclic core of batrachotoxin and select batrachotoxin analogue designs

Iridium‐Catalyzed, Silyl‐Directed, peri‐Borylation of C−H Bonds in Fused Polycyclic Arenes and Heteroarenes

Synthesis and structure of salts of a sterically shielded, lipophilic, C2-symmetric, fluxional aluminate

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