Highly enantioselective synthesis of silahelicenes using Ir-catalyzed [2+2+2] cycloaddition

Shibata, Takanori; Uchiyama, Toshifumi; Yoshinami, Yusuke; Takayasu, S.; Tsuchikama, Kyoji; Endo, Kohei

doi:10.1039/c1cc16762f

Cited by 100 publications

(43 citation statements)

References 37 publications

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“…[4a], [10], and [28]) in the asymmetric synthesis of helicenes by transition-metal-catalyzed [2+2+2] alkyne cycloisomerization, and developed a straightforward approach to the optically pure paradigmatic dibenzo [6]helicene.…”

Section: Methodsmentioning

confidence: 99%

“…Nowadays, the intra/intermolecular [2+2+2] cycloisomerization of alkynes has been established as a standard method for the synthesis of helical (hetero)aromatics as reported by our group, [7] Vollhardt et al, [8] Teplý et al, [9] Tanaka et al, [4a] Shibata et al, [10] Carbery et al, [11] and Diederich et al [12] By utilizing this methodology, we previously carried out the direct cycloisomerization of aromatic Z,Z dienetriynes into helicenes (4!5; Scheme 1). [7d] As this method of helicene synthesis has limits in the chemical stability (and accessibility) of the starting Z,Z dienetriynes, we propose herein their stabilized analogues as exemplified by 4 where the (Z)-1,2vinylene fragments are embedded in the ortho-phenylene moieties.…”

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confidence: 99%

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Rapid Access to Dibenzohelicenes and their Functionalized Derivatives

et al. 2013

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Spiraling up: Easy access to dibenzo[5]-, dibenzo[6]-, and dibenzo[7]helicenes as well as their functionalized derivatives includes Sonogashira and Suzuki-Miyaura couplings, desilylation, and [2+2+2] alkyne cycloisomerization. The simplicity of this non-photochemical approach combined with the potential for helicity control favors dibenzohelicenes over the parent helicenes for practical applications.

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Section: Methodsmentioning

confidence: 99%

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confidence: 99%

Rapid Access to Dibenzohelicenes and their Functionalized Derivatives

et al. 2013

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“…Furthermore, following the pioneering work of Tamao, Yamaguchi et al, new synthetic pathways have been developed to prepare silole-containing polyacenes B (Figure 1), namely Si-containing ladder-π-conjugated systems [28][29][30][31][32][33][34][35][36]. Others families of fused silole derivatives such as Si-containing helicenes [37,38] and small 2D Polycyclic Aromatic Hydrocarbons (PAHs) [39] were also recently prepared. Other than the synthetic challenge of preparing these derivatives, they appeared highly emissive in solution.…”

Section: Introductionmentioning

confidence: 99%

Blue Electrofluorescence Properties of Furan–Silole Ladder Pi-Conjugated Systems

et al. 2018

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Abstract:A synthetic route to novel benzofuran fused silole derivatives is described and the new compounds were fully characterized. These compounds showed optical and electrochemical properties that differ from their benzothiophene analog. Preliminary results show that these derivatives can be used as blue emitters in organic light emitting devices (OLEDs) illustrating the potential of these new compounds for opto-electronic applications.

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“…[102] In terms of yields and enantioselectivities, the second system is the most successful, with almost complete chirality transfer (Scheme 48). The methodology is based on a two-step procedure involving either iridium or iridium/nickel catalysis.…”

Section: Iridium Catalysismentioning

confidence: 99%

Recent Advances in Stereoselective [2+2+2] Cycloadditions

2014

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The [2+2+2] cycloaddition reaction is considered one of the most efficient methods for the rapid and straightforward preparation of complex polycyclic (and heterocyclic) compounds in a highly selective and atom‐economical fashion. Over the last half‐century, remarkable advances in terms of chemo‐ and regioselectivities have been realized, endowing this reaction with attractive features as a key step in the synthesis of various biologically active molecules and materials. The development of stereoselective methodologies is more recent. In this field, asymmetric transition‐metal catalysis has emerged as the most convenient tool with which to perform these [2+2+2] cycloadditions in their enantio‐ and diastereoselective variants. All the catalytic systems that have been developed so far are based on very close association of a transition metal (Co, Ni, Ir, Rh, ...) with a chiral ligand. The success of these reactions is then related to the reaction pattern involved (inter‐ and intramolecular), implying an efficient substrate/active species interaction. Thus, judicious design both of chiral ligands and of unsaturated substrates is necessary. In light of these aspects, numerous stereoselective cycloadditions have been reported; these allow the construction in one‐step fashion of central, axial, planar, and helical chiralities. This review details the recent advances in this area, with specific attention to catalysts and reaction scope.

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Highly enantioselective synthesis of silahelicenes using Ir-catalyzed [2+2+2] cycloaddition

Cited by 100 publications

References 37 publications

Rapid Access to Dibenzohelicenes and their Functionalized Derivatives

Rapid Access to Dibenzohelicenes and their Functionalized Derivatives

Blue Electrofluorescence Properties of Furan–Silole Ladder Pi-Conjugated Systems

Recent Advances in Stereoselective [2+2+2] Cycloadditions

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