Total synthesis of dendrobate alkaloid (+)-241D, isosolenopsin and isosolenopsin A: application of a gold-catalyzed cyclization

Gouault, Nicolas; Roch, Myriam Le; Pinto, Gisele de Campos; David, Michèle

doi:10.1039/c2ob25685a

Cited by 35 publications

(21 citation statements)

References 33 publications

(28 reference statements)

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“…(+)‐Isosolenopsin [(2 S ,6 R )‐ 1a ] was obtained as a colourless solid in 98 % yield (38.5 mg, 0.15 mmol) over two steps. Analytical data are in full agreement with those previously published 6a. M.p.…”

Section: Methodssupporting

confidence: 90%

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Control of the Helical Chirality of Enantiopure Sulfinyl (Z)‐Azobenzene‐Based Photoswitches

Núñez

Merino

Lecea

et al. 2013

Chemistry A European J

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A new class of enantiopure ortho,ortho-disubstituted azobenzene photoswitches has been synthesized from (S)-2-(p-tolylsulfinyl)benzoquinone and arylhydrazines. The sulfoxide acts as a unidirectional controller of the helical chirality that arises in the Z isomer after photoisomerization. Highly congested E-azobenzenes 5 c showed two atropisomeric diastereoconformers in the solid state that converged upon irradiation into a unique Z isomer with defined helicity (M), as evident in the X-ray structure. The chiroptical properties of this three-state enantiopure switch can be externally tuned both photochemically and/or thermally. Theoretical CD spectra calculated by using time-dependent DFT methods support the existence of two atropoisomeric E isomers and only one Z isomer with (M) helicity. Complementary to the classical azobenzene-based switches, the photoswiching event is promoted under green/blue light and do not occur under UV irradiation.

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Section: Methodssupporting

confidence: 90%

“…[ α ] D 20 = –9.0 ( c = 1.0, CHCl 3 , ee > 99 %, de > 98 %); Lit. :6a [ α ] D 25 = +11.1 ( c = 1.02, CHCl 3 ) for the opposite enantiomer.…”

Section: Methodsmentioning

confidence: 99%

Control of the Helical Chirality of Enantiopure Sulfinyl (Z)‐Azobenzene‐Based Photoswitches

Núñez

Merino

Lecea

et al. 2013

Chemistry A European J

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“…Gouault et al accomplished the asymmetric total synthesis of dendrobate alkaloid (+)-241D (74) and isosolenopsin (76) (Scheme 15) [46][47][48]. Structurally, these alkaloids consist of cis-2,6-dialkylpiperidine.…”

Section: Chiral Pool: Alaninementioning

confidence: 99%

Recent Advances in Substrate-Controlled Asymmetric Induction Derived from Chiral Pool α-Amino Acids for Natural Product Synthesis

Paek

Jeong

et al. 2016

Molecules

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Chiral pool α-amino acids have been used as powerful tools for the total synthesis of structurally diverse natural products. Some common naturally occurring α-amino acids are readily available in both enantiomerically pure forms. The applications of the chiral pool in asymmetric synthesis can be categorized prudently as chiral sources, devices, and inducers. This review specifically examines recent advances in substrate-controlled asymmetric reactions induced by the chirality of α-amino acid templates in natural product synthesis research and related areas.

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“…Several racemic and asymmetric total syntheses have been reported based on chiral pool precursors and catalytic (asymmetric) transformations, in addition to electrochemical and auxiliary controlled methods 6. Although several routes are very elegant and involve highly sophisticated key steps, the long reaction sequences and the use of an orthogonal protecting-group strategy has hampered their overall efficiency.…”

Section: Introductionmentioning

confidence: 99%

Concise Chemoenzymatic Three‐Step Total Synthesis of Isosolenopsin through Medium Engineering

et al. 2013

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A short and efficient total synthesis of the alkaloid isosolenopsin and its enantiomer has been achieved. The key step was a ω-transaminase-catalysed regioselective monoamination of the diketone pentadecane-2,6-dione, which was obtained in a single step through the application of a Grignard reaction. Initial low conversions in the biotransformation could be overcome by optimisation of the reaction conditions employing suitable cosolvents. In the presence of 20 vol.-% N,N-dimethylformamide (DMF) or n-heptane the best results were obtained by employing two enantiocomplementary ω-transaminases originating from Arthrobacter at 30–40 °C; under these conditions, conversions of more than 99 % and perfect stereocontrol (ee > 99 %) were achieved. Diastereoselective chemical reduction (H2/Pd/C) of the biocatalytic product gave the target compound. The linear three-step synthesis provided the natural product isosolenopsin in diastereomerically pure form (ee > 99 %, dr = 99:1) with an overall yield of 64 %.

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Total synthesis of dendrobate alkaloid (+)-241D, isosolenopsin and isosolenopsin A: application of a gold-catalyzed cyclization

Cited by 35 publications

References 33 publications

Control of the Helical Chirality of Enantiopure Sulfinyl (Z)‐Azobenzene‐Based Photoswitches

Control of the Helical Chirality of Enantiopure Sulfinyl (Z)‐Azobenzene‐Based Photoswitches

Recent Advances in Substrate-Controlled Asymmetric Induction Derived from Chiral Pool α-Amino Acids for Natural Product Synthesis

Concise Chemoenzymatic Three‐Step Total Synthesis of Isosolenopsin through Medium Engineering

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