Bromination of Cycloparaphenylenes: Strain‐Induced Site‐Selective Bis‐Addition and Its Application for Late‐Stage Functionalization

Kayahara, Eiichi; Qu, Rui; Yamago, Shigeru

doi:10.1002/anie.201704982

Cited by 52 publications

(33 citation statements)

References 71 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The synthesis of a [10]CPP derivative bearing a functional group that would allow mild and efficient cross‐coupling reactions marked the start of this study. To our disappointment, we were unable to transform [10]CPP directly into bromo‐ or iodo‐[10]CPP, which is in agreement with a recent study on the bromination of highly strained [ n ]CPPs ( n ≤8) . Hence, we decided to use a trimethylsilyl (TMS) group as a functional handle that would allow the late‐stage introduction of an iodo substituent.…”

Section: Figurementioning

confidence: 70%

A Supramolecular [10]CPP Junction Enables Efficient Electron Transfer in Modular Porphyrin–[10]CPP⊃Fullerene Complexes

et al. 2018

View full text Add to dashboard Cite

Efficient photoinduced electron transfer was observed across a [10]cycloparaphenylene ([10]CPP) moiety that serves as a rigid non-covalent bridge between a zinc porphyrin and a range of fullerenes. The preparation of iodo-[10]CPP is the key to the synthesis of a porphyrin-[10]CPP conjugate, which binds C , C , (C ) , and other fullerenes (K >10 m ). Fluorescence and pump-probe spectroscopy revealed intramolecular energy transfer between CPP and porphyrin and also efficient charge separation between porphyrin and fullerenes, affording up to 0.5 μs lifetime charge-separated states. The advantage of this approach towards electron donor-acceptor dyads is evident in the case of dumbbell-shaped (C ) , which gave intricate charge-transfer behavior in 1:1 and 2:1 complexes. These results suggest that [10]CPP and its cross-coupled derivatives could act as supramolecular mediators of charge transport in organic electronic devices.

show abstract

Section: Figurementioning

confidence: 70%

A Supramolecular [10]CPP Junction Enables Efficient Electron Transfer in Modular Porphyrin–[10]CPP⊃Fullerene Complexes

et al. 2018

View full text Add to dashboard Cite

show abstract

“…[12] Thesynthesis of a [10]CPP derivative bearing afunctional group that would allow mild and efficient cross-coupling reactions marked the start of this study.T oo ur disappointment, we were unable to transform [10]CPP directly into bromo-or iodo- [10]CPP,which is in agreement with arecent study on the bromination of highly strained [n]CPPs (n 8). [13] Hence,w ed ecided to use at rimethylsilyl (TMS) group as af unctional handle that would allow the late-stage introduction of an iodo substituent. As shown in Scheme 1( top), our successful synthesis of iodo- [10]CPP follows Jastisreported synthesis of [10]CPP, [14] with some crucial deviations,s uch as the use of am ethoxymethyl protecting group (MOM) in the sixth step of the sequence (2,S cheme 1).…”

mentioning

confidence: 99%

A Supramolecular [10]CPP Junction Enables Efficient Electron Transfer in Modular Porphyrin–[10]CPP⊃Fullerene Complexes

Wang

Kaur

et al. 2018

Angewandte Chemie

View full text Add to dashboard Cite

Efficient photoinduced electron transfer was observed across a[ 10]cycloparaphenylene ([10]CPP) moiety that serves as ar igid non-covalent bridge between az inc porphyrin and ar ange of fullerenes.The preparation of iodo-[10]CPP is the key to the synthesis of ap orphyrin-[10]CPP conjugate,w hich binds C 60 ,C 70 ,( C 60 ) 2 ,a nd other fullerenes (K A > 10 5 m À1 ). Fluorescence and pump-probe spectroscopy revealed intramolecular energy transfer between CPP and porphyrin and also efficient charge separation between porphyrin and fullerenes,a ffording up to 0.5 msl ifetime chargeseparated states.T he advantage of this approach towards electron donor-acceptor dyads is evident in the case of dumbbell-shaped (C 60 ) 2 ,w hichg ave intricate charge-transfer behavior in 1:1a nd 2:1c omplexes.T hese results suggest that [10]CPP and its cross-coupled derivatives could act as supramolecular mediators of charge transport in organic electronic devices.

show abstract

“…[12] Theg ram-scale synthesis of CPPs also opens an ew possibility to study their reactivities and the synthesis of their derivatives by late-stage functionalization. [13] As apart of our ongoing studies to elucidate the reactivity of CPPs,w e became interested in the reaction of CPP with at ransitionmetal complex (Scheme 1). Of the possible reactions between CPP and metal complexes,t hat is, p-complexation, CÀH insertion, and C À Cinsertion, the C À Cinsertion is among the most interesting because it significantly alters the electronic structures of the CPP and can lead to the synthesis of new cyclic p-conjugated molecules.W hile two examples of reactions between CPPs and transition-metal complexes were reported by the groups of Itami [13a] and Yamago, [14] only p-complexes were observed.…”

mentioning

confidence: 99%

Strain‐Induced Double Carbon–Carbon Bond Activations of Cycloparaphenylenes by a Platinum Complex: Application to the Synthesis of Cyclic Diketones

et al. 2018

Self Cite

View full text Add to dashboard Cite

The carbon-carbon (CÀC) bond activation of [n]cycloparaphenylenes ([n]CPPs) by atransition-metal complex is herein reported. The Pt 0 complex Pt(PPh 3 ) 4 regioselectively cleaves two C À C s bonds of [5] CPP and [6]CPP to give cyclic dinuclear platinum complexes in high yields.Theoretical calculations reveal that the relief of ring strain drives the reaction. The cyclic complex was further transformed into acyclic diketone by using aCOinsertion reaction.Cycloparaphenylenes (CPPs;S cheme 1) have attracted immense scientific interest because of their fascinating structure,p hysical properties,a nd potential applications in materials science.T his interest originates from their nonplanar and conjugated structure corresponding to the shortest cyclic structural unit of an armchair carbon nanotube. [1] After the successful bottom-up organic synthesis of CPPs by Jasti and Bertozzi et al., [2] Itami et al., [3] and Yamago et al., [4] CPPs of various sizes, [5][6][7] and their derivatives, [8] are available,a nd their unique physical properties,s uch as size-dependent photophysical [9] and redox properties [7a, 10] and host-guest chemistry, [11] have been unveiled. In particular, recent achievements in the large-scale synthesis of CPPs by the groups Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.org/10.1002/anie.201806591. Scheme 1. Possible reactions of [n]CPP with atransition-metal complex. Ma nd Ld enote metal and ligand, respectively. Scheme 2. The CÀCactivation of [n]CPPs and subsequent transformation.

show abstract

Bromination of Cycloparaphenylenes: Strain‐Induced Site‐Selective Bis‐Addition and Its Application for Late‐Stage Functionalization

Cited by 52 publications

References 71 publications

A Supramolecular [10]CPP Junction Enables Efficient Electron Transfer in Modular Porphyrin–[10]CPP⊃Fullerene Complexes

A Supramolecular [10]CPP Junction Enables Efficient Electron Transfer in Modular Porphyrin–[10]CPP⊃Fullerene Complexes

A Supramolecular [10]CPP Junction Enables Efficient Electron Transfer in Modular Porphyrin–[10]CPP⊃Fullerene Complexes

Strain‐Induced Double Carbon–Carbon Bond Activations of Cycloparaphenylenes by a Platinum Complex: Application to the Synthesis of Cyclic Diketones

Contact Info

Product

Resources

About