Asymmetric Allenophanes: Synthesis of a Tris‐<i>meta</i>‐allenophane and Tetrakis‐<i>meta</i>‐allenophane by Sequential Cross‐Coupling

Leclère, Mathieu; Fallis, Alex G.

doi:10.1002/ange.200703003

Cited by 17 publications

(5 citation statements)

References 44 publications

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“…As it was mentioned in the introduction, the synthesis of allenylphosphonates via a sigmatropic rearrangement occurs with stereospecificity of the allenyl moiety formation. Taking into account an easy access to highly enantiomerically enriched propargylic alcohols34 (e.g., from enzymatic kinetic resolution35 or stereoselective addition to aldehydes36) this feature would be beneficial in the synthesis of complex allenylphosphonate derivatives. Therefore, we set out to investigate if the palladium‐catalyzed reaction also can compete with the sigmatropic rearrangement method in this respect.…”

Section: Resultsmentioning

confidence: 99%

Novel, Stereoselective and Stereospecific Synthesis of Allenylphosphonates and Related Compounds via Palladium‐Catalyzed Propargylic Substitution

Kalek

Stawiński

2011

Adv Synth Catal

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Abstract:We have developed a novel method for the synthesis of allenylphosphonates and related compounds based on a palladium(0)-catalyzed reaction of propargylic derivatives with H-phosphonate, H-phosphonothioate, H-phosphonoselenoate, and Hphosphinate esters. The reaction is stereoselective and stereospecific, and provides a convenient entry to a vast array of allenylphosphonates and their analogues with diverse substitution patterns in the allenic moiety and at the phosphorus center. Some mechanistic aspects of this new reaction were also investigated.

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Section: Resultsmentioning

confidence: 99%

Novel, Stereoselective and Stereospecific Synthesis of Allenylphosphonates and Related Compounds via Palladium‐Catalyzed Propargylic Substitution

Kalek

Stawiński

2011

Adv Synth Catal

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“…Leclère and Fallis reported meta ‐allenophanes ( P , P , P )‐(−)‐ 13 a and ( P , P , P , P )‐(−)‐ 13 b (Scheme ) 48. Although these allenophanes are very unstable, the ECD spectra were measured, and showed Cotton effects around 260 nm ((Δ ε =+20 M −1 cm −1 ) for ( P , P , P , P )‐(−)‐ 13 b and (Δ ε =+5 M −1 cm −1 ) for ( P , P , P )‐(−)‐ 13 a ).…”

Section: Allenophanes and Alleno‐acetylenic Macrocyclesmentioning

confidence: 99%

Allenes in Molecular Materials

2012

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This Minireview provides a critical account of the development of allene-containing advanced functional materials, starting with the design and synthesis of stable and enantiopure building blocks. A variety of systems, including shape-persistent macrocycles, foldamers, polymers, charge-transfer chromophores, dendrimers, liquid crystals, and redox-switchable chiral chromophores are discussed from the viewpoint of their syntheses, properties, and potential applications. The goal of this Minireview is to inspire new uses of enantiopure allenes for the rational design of advanced materials.

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“…22,23 Allenes due to their axial chirality and synthetic versatility are a unique family of organic molecules and can participate in a diverse range of reactions. 24 The chemistry of allenes has experienced a great advancement in the 20th century, as summarized in the monographs by Schuster and Coppola 25 and more recently by Krause and Hashmi. 26 Modern synthetic methods allow the construction of allenes with a wide variety of substituents.…”

Section: Introductionmentioning

confidence: 99%

Nonplanar Donor–Acceptor Chiral Molecules with Large Second-Order Optical Nonlinearities: 1,1,4,4-Tetracyanobuta-1,3-diene Derivatives

Yang

2014

J. Phys. Chem. A

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We have investigated the chiroptical, linear, and second-order nonlinear optical (NLO) properties of five 1,1,4,4-tetracyanobuta-1,3-diene (TCBD) derivatives and elucidated structure-property relationships from the micromechanism. The experimental UV-vis absorption and circular dichroism (CD) spectra were well reproduced by our calculations at TDB3LYP/6-31+G* level of theory. The electron transition property and chiroptical origin have been assigned and analyzed. The results show that the studied compounds possess large molecular first hyperpolarizabilities, especially for compound 5 which has a value of 35 × 10(-30) esu, which is comparable with the measured value for highly π-delocalized phenyliminomethyl ferrocene complex and about 200 times larger than the average first hyperpolarizability of the organic urea molecule. Despite the nonplanarity of these compounds, efficient intramolecular charge transfer (CT) from electron donor to electron acceptor moieties was observed, which plays the key role in determining the NLO response. The intramolecular charge transfer cooperativity was also probed. In view of the first hyperpolarizability values, intrinsic noncentrosymmetric electronic structure, and high stability, the studied compounds have the possibility to be excellent second-order NLO materials.

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Asymmetric Allenophanes: Synthesis of a Tris‐meta‐allenophane and Tetrakis‐meta‐allenophane by Sequential Cross‐Coupling

Cited by 17 publications

References 44 publications

Novel, Stereoselective and Stereospecific Synthesis of Allenylphosphonates and Related Compounds via Palladium‐Catalyzed Propargylic Substitution

Novel, Stereoselective and Stereospecific Synthesis of Allenylphosphonates and Related Compounds via Palladium‐Catalyzed Propargylic Substitution

Allenes in Molecular Materials

Nonplanar Donor–Acceptor Chiral Molecules with Large Second-Order Optical Nonlinearities: 1,1,4,4-Tetracyanobuta-1,3-diene Derivatives

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