Enantioselective Synthesis of Distorted π‐Extended Chiral Triptycenes Consisting of Three Distinct Aromatic Rings by Rhodium‐Catalyzed [2+2+2] Cycloaddition

Aida, Yuta; Shibata, Yu; Tanaka, Ken

doi:10.1002/chem.201905519

Cited by 15 publications

(7 citation statements)

References 54 publications

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“…Unfortunately, treatment of pentylene‐tethered chiral macrocycle 20 e with DDQ failed to afford the corresponding fluorenone‐based cyclophane 21 e and led to an unidentified mixture of products (entry 6). The undesired strain‐relieving carbocation rearrangement might proceed in the oxidation of 20 e with DDQ . Thus, Esser's dehydrative aromatization method using the Burgess reagent [methyl N ‐(triethylammoniumsulfonyl)carbamate], in which no carbocations are formed, is advantageous for the aromatization of highly bent structures .…”

Section: Resultsmentioning

confidence: 99%

Enantioselective Synthesis of Polycyclic Aromatic Hydrocarbon (PAH)‐Based Planar Chiral Bent Cyclophanes by Rhodium‐Catalyzed [2+2+2] Cycloaddition

Aida

Nogami

Sugiyama

et al. 2020

Chemistry A European J

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The enantioselective synthesis of polycyclic aromatic hydrocarbon (PAH)-based planar chiral cyclophanes was achieved for the first time by the rhodium-catalyzed intramolecular regio-and enantioselective [2+ +2+ +2] cycloaddition of tethered diyne-benzofulvenes followed by stepwise oxidative transformations. The thus synthesized planarc hiral bent cyclophanes, that possess bent p-terphenyl-and 9-fluorenone-cores, were converted to 9-fluorenol-based ones with excellent ee values of > 99 %b yd iastereoselective 1,2-reduction.T hese 9-fluorenol-based cyclophanes exhibited high fluorescenceq uantum yields, which were significantly highert han that of an acyclicr eference molecule (78-82 % vs. 48 %). The bending effect on the chiropticalp roperty was also examined, whichr evealed that the anisotropy factors (g abs values) for electronic circular dichroism (ECD) of these 9-fluorenol-based planar chiral bent cyclophanes increasea s the tether length becomes shorter.

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Section: Resultsmentioning

confidence: 99%

Enantioselective Synthesis of Polycyclic Aromatic Hydrocarbon (PAH)‐Based Planar Chiral Bent Cyclophanes by Rhodium‐Catalyzed [2+2+2] Cycloaddition

Aida

Nogami

Sugiyama

et al. 2020

Chemistry A European J

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“…The reaction proceeded using cationic Rh(I)/(R)-SEGPHOS complex to access distorted -extended chiral triptycenes, consisting of three distinct aromatic rings, in 63->99% yield and up to 88% ee (Scheme 33). 95 In this approach, the use of electron-deficient diyne and electron-rich alkene was essential to suppress the undesired carbocation rearrangement and stabilize the distorted triptycene structure.…”

Section: Review Synthesismentioning

confidence: 99%

Recent Progress in Metal-Catalyzed [2+2+2] Cycloaddition Reactions

Matton¹,

Huvelle²,

Haddad³

et al. 2021

Synthesis

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Metal-catalyzed [2+2+2] cycloaddition is a powerful tool that allows rapid construction of functionalized 6-membered carbo- and heterocycles in a single step through an atom-economical process with high functional group tolerance. The reaction is usually regio- and chemoselective although selectivity issues can still be challenging for intermolecular reactions involving the cross-[2+2+2] cycloaddition of two or three different alkynes and various strategies have been developed to attain high selectivities. Furthermore, enantioselective [2+2+2] cycloaddition is an efficient means to create central, axial, and planar chirality and a variety of chiral organometallic complexes can be used for asymmetric transition-metal-catalyzed inter- and intramolecular reactions. This review summarizes the recent advances in the field of [2+2+2] cycloaddition.1 Introduction2 Formation of Carbocycles2.1 Intermolecular Reactions2.1.1 Cyclotrimerization of Alkynes2.1.2 [2+2+2] Cycloaddition of Two Different Alkynes2.1.3 [2+2+2] Cycloaddition of Alkynes/Alkenes with Alkenes/Enamides2.2 Partially Intramolecular [2+2+2] Cycloaddition Reactions2.2.1 Rhodium-Catalyzed [2+2+2] Cycloaddition2.2.2 Molybdenum-Catalyzed [2+2+2] Cycloaddition2.2.3 Cobalt-Catalyzed [2+2+2] Cycloaddition2.2.4 Ruthenium-Catalyzed [2+2+2] Cycloaddition2.2.5 Other Metal-Catalyzed [2+2+2] Cycloaddition2.3 Totally Intramolecular [2+2+2] Cycloaddition Reactions3 Formation of Heterocycles3.1 Cycloaddition of Alkynes with Nitriles3.2 Cycloaddition of 1,6-Diynes with Cyanamides3.3 Cycloaddition of 1,6-Diynes with Selenocyanates3.4 Cycloaddition of Imines with Allenes or Alkenes3.5 Cycloaddition of (Thio)Cyanates and Isocyanates3.6 Cycloaddition of 1,3,5-Triazines with Allenes3.7 Cycloaddition of Aldehydes with Enynes or Allenes/Alkenes3.8 Totally Intramolecular [2+2+2] Cycloaddition Reactions4 Conclusion

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“…In 2015, the first enantioselective synthesis of chiral triptycene was reported by Shibata [ 141 ]. Another one was recently presented by Aida [ 142 ], who proposed a strategy that starts from the preparation of chiral multicyclic cyclohexadienes. A set of such compounds was obtained by a highly enantioselective [2 + 2 + 2] cycloaddition between 2,2′-di(prop-1-yn-1-yl)-1,1′-biphenyls and 1,2-dihydronaphthalenes ( Scheme 8 ).…”

Section: Progress In Triptycene Synthesis and Derivatizationmentioning

confidence: 99%

Triptycene Derivatives: From Their Synthesis to Their Unique Properties

2021

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Since the first preparation of triptycene, great progress has been made with respect to its synthesis and the understanding of its properties. Interest in triptycene-based systems is intense; in recent years, advances in the synthetic methodology and properties of new triptycenes have been reported by researchers from various fields of science. Here, an account of these new developments is given and placed in reference to earlier pivotal works that underpin the field. First, we discuss new approaches to the synthesis of new triptycenes. Progress in the regioselective synthesis of sterically demanding systems is discussed. The application of triptycenes in catalysis is also presented. Next, progress in the understanding of the relations between triptycene structures and their properties is discussed. The unique properties of triptycenes in the liquid and solid states are elaborated. Unique interactions, which involve triptycene molecular scaffolds, are presented. Molecular interactions within a triptycene unit, as well as between triptycenes or triptycenes and other molecules, are also evaluated. In particular, the summary of the synthesis and useful features will be helpful to researchers who are using triptycenes as building blocks in the chemical and materials sciences.

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Enantioselective Synthesis of Distorted π‐Extended Chiral Triptycenes Consisting of Three Distinct Aromatic Rings by Rhodium‐Catalyzed [2+2+2] Cycloaddition

Cited by 15 publications

References 54 publications

Enantioselective Synthesis of Polycyclic Aromatic Hydrocarbon (PAH)‐Based Planar Chiral Bent Cyclophanes by Rhodium‐Catalyzed [2+2+2] Cycloaddition

Enantioselective Synthesis of Polycyclic Aromatic Hydrocarbon (PAH)‐Based Planar Chiral Bent Cyclophanes by Rhodium‐Catalyzed [2+2+2] Cycloaddition

Recent Progress in Metal-Catalyzed [2+2+2] Cycloaddition Reactions

Triptycene Derivatives: From Their Synthesis to Their Unique Properties

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