Triflic Acid-Promoted Adamantylation and <i>tert</i>-Butylation of Pyrene: Fluorescent Properties of Pyrene-Decorated Adamantanes and a Channeled Crystal Structure of 1,3,5-Tris(pyren-2-yl)adamantane

Wrona-Piotrowicz, Anna; Makal, Anna

doi:10.1021/acs.joc.0c01060

Cited by 15 publications

(10 citation statements)

References 31 publications

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“…In 1 H NMR, a singlet is observed at 7.96 ppm for the β-H 9 in 2. Consistently, a similar 1 H NMR pattern was observed for all the 10-arylated pyrenylphosphines (2)(3)(4)(5)(6)(7)(8)(9)(10)(11)(12)(13)(14)(15)(16)(17)(18)(19).…”

Section: Resultssupporting

confidence: 75%

“…Alternatively, alkylation by aluminum reagents, [6] reactions with triflic acid, [7] and iridium-catalyzed borylation [8] occurs at 2-or 7-positions (Scheme 1). Conversely, the synthesis of pyrene derivatives substituted at the K-region (4-, 5-, 9-and 10-positions) Scheme 1.…”

Section: Introductionmentioning

confidence: 99%

“…Alternatively, alkylation by aluminum reagents, [6] reactions with triflic acid, [7] and iridium‐catalyzed borylation [8] occurs at 2‐ or 7‐positions (Scheme 1). Conversely, the synthesis of pyrene derivatives substituted at the K ‐region (4‐, 5‐, 9‐ and 10‐positions) usually requires tedious multistep metalation and halogenation procedures, which results in general in low overall yields [9] .…”

Section: Introductionmentioning

confidence: 99%

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Phosphorus‐Directed Rhodium‐Catalyzed C−H Arylation of 1‐Pyrenylphosphines Selective at the K‐Region

et al. 2021

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CÀ H arylation of 1-pyrenylphosphine derivatives catalyzed by rhodium and directed by a diphenylphosphino group is selectively achieved at the K-region, i. e. 4-, 5-, 9-, or 10-position of the pyrene moiety. This peri CÀ H activation/arylation of pyrenes using (hetero)aryl bromide coupling partners tolerates both electron-donating and electron-withdrawing groups on the arene, and provides isolated yields of products between 25% to 90%, including from bulky polyaromatic bromoarene substrates. We achieved investigations directed at the formation and reactivity of pertinent intermediate species in this CÀ H arylation reaction. The P-ligand coordination at rhodium was established using 31 P NMR and XRD analysis, and we isolated five-membered rhodacycles as intermediates to the directed CÀ H functionalization. The data obtained overall supported the occurrence of a cationic rhodium catalytic process. We further described the access to a large class of pyrenylphosphine ligands and their selenated derivatives. Phosphine selenation allows to rapidly estimate from 1 J P = Se values the basic character of the ligand in the perspective of their use for coordination. Accordingly, linear P-coordinated Au(I) gold complexes were isolated, in addition to the variously coordinated Rh(III) complexes. The present methodology significantly extends the scope of polyaromatics that are functionalizable at the K-Region by direct CÀ H activation, beyond smaller-sized naphtalenes and aminopyrenes.

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Section: Resultssupporting

confidence: 75%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Phosphorus‐Directed Rhodium‐Catalyzed C−H Arylation of 1‐Pyrenylphosphines Selective at the K‐Region

et al. 2021

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“…37 On the level of synthetic applications, iTIM and iTBro are interesting building blocks, as they offer access to cross coupling products extending the aryl arms in Pd-catalyzed synthetic transformations. 38 Both should be suitable for a range of different reaction partners and conditions, so that structurally interesting, large and rigid target molecules 39 may be prepared based on these TAAs that are now accessible in high yield and purity.…”

Section: Feature Synthesismentioning

confidence: 99%

Kinetic or Thermodynamic Product? Case Studies on the Formation of Regioisomers of Tetraphenyladamantanes

Richert¹,

Frey²,

Berking³

2023

Synthesis

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Tetraaryldamantanes (TAAs) with alkoxyphenyl groups are interesting synthetic targets because they can act as crystallization chaperones for liquid compounds. Their carbon framework is set up by Friedel-Crafts alkylation, using adamantane-1,3,5,7-tetraol and anisole derivatives as starting materials. One successful chaperone is 1,3,5,7-tetrakis(2-bromo-4-methoxyphenyl)adamantane (TBro). This compound was initially considered the thermodynamic product of alkylation. We now report that exposure of TBro to strong Brønsted acid leads to its regioisomer 1,3,5,7-tetrakis(4-bromo-2-methoxyphenyl)adamantane (iTBro) as the dominant product, obtained in a yield of 68%, far surpassing the 20% yield reported earlier for TBro. We also investigated the reactions of 3-iodo-, 3-chloro-, and 3-fluoroanisole to the corresponding TAAs and obtained yields of 66%, 26% and 52% for the main regioisomer. While 3-iodoanisole gave the same regioisomer as bromoanisole, 3-chloroanisole gave complex mixtures and 3-fluoroanisole gave 1,3,5,7-tetrakis(2-fluoro-4-methoxyphenyl)-adamantane (TFM) in 52% yield as the main product. When mixtures of regioisomers were isomerized with an excess of triflic acid, the thermodynamic products were obtained in 76-91%. These results show how subtle effects govern the regioisomeric product distribution of aryladamantanes. They also help to make novel crystallization chaperones accessible in yields.

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“…5−14 For instance, Cheng and co-workers 13 synthesized the low dielectric material 1,3bis[(1,2-dihydro-benzocyclobutene-4-yl)methylvinylsilyloxy]adamantane with a high glass transition temperature, good thermal stability, and high cross-linking density. Anna and coworkers 14 generated 1,3-bis(pyren-2-yl)adamantane by the interaction of pyrene and 1,3-adamantanediol. It is a new fluorophore with potential applications in organic optoelectronic materials.…”

mentioning

confidence: 99%

Practical and Scalable Synthesis of 1,3-Adamantanediol

Hao,

Chen,

Yang

et al. 2024

Org. Process Res. Dev.

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A new method for the efficient synthesis of 1,3-adamantanediol is proposed. It has the advantages of good reaction selectivity, high isolated yield, easy purification, and safe operation. 3-Hydroxyadamantane-1-carboxylic acid reacts first with thionyl chloride to form 1,3-dichloro adamantane, which is then converted to 1,3-adamantanediol in a "triethylamine−water" solution. Three reaction types are involved: chlorination, decarbonylation, and hydrolysis. Under optimal reaction conditions, total isolated yields of up to 95% and purities of up to 99% were achieved. Isolated yields of 100 g per batch have been achieved, with potential for industrial production. We completed the decarbonylation of acyl chloride without the use of a metal catalyst. In addition, the reaction mechanism was investigated by combining experimental data and density functional theory.

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Triflic Acid-Promoted Adamantylation and tert-Butylation of Pyrene: Fluorescent Properties of Pyrene-Decorated Adamantanes and a Channeled Crystal Structure of 1,3,5-Tris(pyren-2-yl)adamantane

Cited by 15 publications

References 31 publications

Phosphorus‐Directed Rhodium‐Catalyzed C−H Arylation of 1‐Pyrenylphosphines Selective at the K‐Region

Phosphorus‐Directed Rhodium‐Catalyzed C−H Arylation of 1‐Pyrenylphosphines Selective at the K‐Region

Kinetic or Thermodynamic Product? Case Studies on the Formation of Regioisomers of Tetraphenyladamantanes

Practical and Scalable Synthesis of 1,3-Adamantanediol

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