Buta‐2,3‐<scp>dien</scp>‐1‐<scp>ol</scp>

Luoa, Hongwen; Mab, Dengke

doi:10.1002/0471264229.os094.12

Cited by 2 publications

(2 citation statements)

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“…(2) under high-pressure autoclave conditions, 10 mol % of CuI was enough to obtain a better result (Scheme 6). 12,14 Additionally, we had also successfully demonstrated two improved CuI-mediated ATA reactions to synthesize carbohydrate-based terminal allenes in moderate to good yields, tolerating functional groups such as ether, ester, amide, and malonate units. Allenyl β-D-glucopyranosides, β-D-galactopyranoside, thioglycosides, disaccharides, and even pentakisallenyl β-D-glucopyranoside could all be synthesized by applying these two methods (Scheme 7).…”

Section: Synthesis Of Monosubstituted Allenes Via Ata Reactions With ...mentioning

confidence: 99%

Allenation of Terminal Alkynes with Aldehydes and Ketones

Huang

2019

Acc. Chem. Res.

228

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Conspectus So far, over 150 natural products and pharmaceuticals containing an allene moiety have been identified. During the last two decades, allenes have also been demonstrated as synthetically versatile starting materials in organic synthesis. In comparison to alkenes and alkynes, allenes are unique unsaturated hydrocarbons due to their axial chirality, which could be transformed to central chirality via chirality transfer to provide an irreplaceable entry to chiral molecules. Thus, methods for allene synthesis from readily available chemicals are of great interest. In 1979, Crabbé et al. reported the first CuBr-mediated allenation of terminal alkynes (ATA) reaction to form monosubstituted allenes from 1-alkynes and paraformaldehyde in the presence of diisopropylamine. During the following 30 years, the ATA reactions were limited to paraformaldehyde. This Account describes our efforts toward the development of ATA reactions in the last ten years. First, we improved the yields and scope greatly for the synthesis of monosubstituted allenes by modifying the original Crabbé recipe. Next we developed the ZnI2-promoted or CuI-catalyzed ATA reactions for the synthesis of 1,3-disubstituted allenes from terminal alkyne and normal aldehydes. Furthermore, we first realized the CdI2-promoted ATA reaction of ketones with pyrrolidine as the matched amine for the preparation of trisubstituted allenes. Due to the toxicity of CdI2, we also developed two alternative approaches utilizing CuBr/ZnI2 or CuI/ZnBr2/Ti(OEt)4. The asymmetric version of ATA reactions for the synthesis of optically active 1,3-disubstituted allenes has also been achieved in this group with two strategies. One is called “chiral ligand” strategy, using terminal alkynes, aldehydes, and nonchiral amine with the assistance of a proper chiral ligand. The other is the “chiral amine” strategy, applying terminal alkynes, aldehydes, and chiral amines such as (S)- or (R)-α,α-diphenylprolinol or (S)- or (R)-α,α-dimethylprolinol. Optically active 1,3-disubstituted allenes containing different synthetically useful functionalities such as alcohol, amide, sulfamide, malonate, carboxylate, and carbohydrate units could be prepared without protection with the newly developed CuBr2-catalyzed chiral amine strategy. Recently, we have applied these enantioselective allenation of terminal alkyne (EATA) reactions to the syntheses of some natural allenes such as laballenic acid, insect pheromone, methyl (R)-8-hydroxyocta-5,6-dienoate, phlomic acid, and lamenallenic acid, as well as some non-allene natural γ-butyrolactones such as xestospongienes (E, F, G, and H), (R)-4-tetradecalactone, (S)-4-tetradecalactone, (R)-γ-palmitolactone, and (R)-4-decalactone.

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Section: Synthesis Of Monosubstituted Allenes Via Ata Reactions With ...mentioning

confidence: 99%

Allenation of Terminal Alkynes with Aldehydes and Ketones

Huang

2019

Acc. Chem. Res.

228

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“…[1][2][3][4][5][6][7][8][9][10] Owing to the surface location of the nanosized cavities, the surface imprinting technique has become one of the most effective ways to improve the preparation of molecularly imprinted polymers (MIP). [11][12][13][14] Surface-imprinted polymer films on a solid substrate exhibit high binding capacities, fast mass transfer, and fast binding kinetics due to their easy access to recognition sites and homogeneous distribution of binding sites. [15][16][17][18][19][20] Here, we describe the use of interface-mediated reversible addition-fragmentation chain transfer (RAFT) polymerization, which is a controllable radical polymerization method, in order to grow ultrathin MIP films on a silicon substrate.…”

Section: Introductionmentioning

confidence: 99%

Ibuprofen‐imprinted ultrathin poly[N‐(2‐hydroxypropyl) methacrylamide] films

Yıldırım

Çaykara

2017

J of Applied Polymer Sci

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Surface molecularly imprinted (MIP) poly [N-(2-hydroxypropyl) methacrylamide] [poly(HPMA)] films were prepared via interface-mediated reversible addition-fragmentation chain transfer (RAFT) polymerization from 4-cyano-4-(propylsulfanylthiocarbonyl) sulfanyl pentanoic acid immobilized silicon substrate using N-(2-hydroxypropyl) methacrylamide as the functional monomer, N,N 0 -methylene(bis)acrylamide as the crosslinking agent, and ibuprofen as the template molecule. The highly crosslinked MIP layer (12 nm) was homogeneously grafted onto the silicon surface, which favors fast mass transfer and rapid binding kinetics. Binding capacities and adsorption parameters of the MIP poly(HPMA) films were calculated from the root-mean-square roughness data obtained by atomic force microscopy measurements using the Luzinov and Langmuir equations adopted for this study. The target binding assays demonstrate the desirable binding capacity and imprinting efficiency of the MIP poly(HPMA) films. Meanwhile, the computational optimization and energy calculations showed the formation of the self-assembly of monomer and template molecule via noncovalent interactions that leads to a 1:4 molecular complex between ibuprofen and N-(2-hydroxypropyl) methacrylamide. This study provides a versatile approach to the quantitative determination of low-molecular-weight biomolecules on surfaceimprinted polymers.

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Buta‐2,3‐dien‐1‐ol

Cited by 2 publications

References 71 publications

Allenation of Terminal Alkynes with Aldehydes and Ketones

Allenation of Terminal Alkynes with Aldehydes and Ketones

Ibuprofen‐imprinted ultrathin poly[N‐(2‐hydroxypropyl) methacrylamide] films

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