Synthesis of 4-Methyldienoates Using a Vinylogous Horner−Wadsworth−Emmons Reagent. Application to the Synthesis of Trichostatic Acid

Schauer, Douglas J.; Löfstedt, Joakim; Corden, Steven J.; Wiest, Olaf; Helquist, Paul

doi:10.1021/jo902422y

Cited by 23 publications

(12 citation statements)

References 50 publications

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“…The residue was recrystallized (9:1 methanol:CH 2 Cl 2 ) to give the title compound as a white solid (88.5 g, 75%). 1 H NMR (CDCl 3 , 300 MHz) δ 0.93 (6H, t, J = 6.8 Hz), 1.30-1.40 (8H, mult), 1.40-1.55 (4H, mult), 1.81 (4H, tt J = 6.8, 6.4 Hz), 3.95 (4H, t, J = 6.4 Hz), 7.09 (2H, s) ppm. 13 C NMR (CDCl 3 ) δ 14.00 (CH 3 ), 22.56 (CH 2 ), 25.59 (CH 2 ), 29.06 (CH 2 ), 31.46 (CH 2 ), 70.26 (OCH 2 ), 111.09 (ArBr quat), 118.41 (Ar CH), 150.04 (ArO quat) ppm.…”

Section: Synthesis Of Monomersmentioning

confidence: 99%

Sequence Matters: Modulating Electronic and Optical Properties of Conjugated Oligomers via Tailored Sequence

et al. 2013

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! Scheme S3. Synthesis of P-B-CN (4). GENERAL METHODS 1 Materials. Anhydrous DMF, n BuLi (1.6 M in hexanes), and DIBAL-H (1.0 M in hexanes) were purchased from Aldrich and dispensed using air-sensitive techniques. Benzoyl peroxide and NBS were stored at-20 o C. KO t Bu was stored in a desiccator over anhydrous CaSO 4. LiCl was dried at 120 o C for at least 24 h. Anhydrous diethyl ether for lithiation reactions was opened immediately prior to use. Reagent grade THF was used for most reactions; notably the HWE reactions used reagent grade THF. DCM for reactions was dried by refluxing with CaH 2. 1,6-1 The general methods section is also found in the paper and is reproduced here for ease of interpreting the experimentals that follow. Supporting information 4 Bis(hexyloxy)benzene (5) was prepared as previously reported. 1 All other reagents (including compounds 7 and 8) and solvents were used as received. Column chromatography was carried out on standard grade silica gel (60 Å pore size, 40-63 µm particle size), which was purchased and used as received. Hexanes, dichloromethane, and ethyl acetate used for column chromatography were purchased and used as received. Melting points for all compounds were determined by DSC and are found in the main text in Table 2, listed as T iso. NMR Spectroscopy. 1 H (300 and 400 MHz) and 13 C (75, 100 and 150 MHz) NMR spectra were recorded on Bruker spectrometers. Chemical shifts were referenced to residual 1 H or 13 C signals in deuterated solvents (7.27 and 77.0 ppm, respectively, for CHCl 3 and 5.32 and 54.0 ppm, respectively, for CH 2 Cl 2). Mass Spectrometry. HRMS were recorded on EI-quadrupole or ESI-TOF instruments in the Mass Spectrometry Facility of the University of Pittsburgh. Optical Spectroscopy. UV/VIS absorption spectra were recorded in CHCl 3 on a Perkin Elmer Lambda 9 UV/VIS/NIR spectrometer. Solution (CHCl 3) and film emission spectra were recorded on a Varian Cary Eclipse fluorimeter. Films were drop cast on quartz slides from CHCl 3. Thermal Analysis. DSC was performed on a Perkin Elmer Pyris 6 with a heating and cooling rate of 10 o C/min. Electrochemistry. Cyclic voltammetry (CV) and differential pulse voltammetry (DPV) were performed on a CHI Electrochemical Workstation Model 430a (Austin, TX) collected using a three electrode system consisting of a glassy carbon disk (3 mm dia.

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Section: Synthesis Of Monomersmentioning

confidence: 99%

Sequence Matters: Modulating Electronic and Optical Properties of Conjugated Oligomers via Tailored Sequence

et al. 2013

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“…Additional studies focused on establishing the stereochemical course of the allylic alkylation through a formal synthesis of trichostatic acid, which is a hydrolysis product of the potent histone deacetylase inhibitor (+)-trichostatin A (Scheme 2C). 23 Oxidative cleavage of the olefin 8b using Jin's modification of the Lemieux-Johnson oxidation, 24 furnished the known aldehyde 10 25 which confirmed the alkylation proceeds via net retention of configuration. Overall, this work represents an important advance for the metal-catalyzed allylic alkylation of secondary allylic alcohol derivatives with an acyl anion equivalent to prepare acyclic α-ternary β,γ-unsaturated aryl ketones in a highly regio- and stereospecific manner.…”

Section: Resultsmentioning

confidence: 93%

Regio- and stereospecific rhodium-catalyzed allylic alkylation with an acyl anion equivalent: an approach to acyclic α-ternary β,γ-unsaturated aryl ketones

et al. 2017

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“…To introduce the desired E,E -diene present in 2 and 1 , we realized that the procedure reported by Markiewicz, comprising a vinylogous Horner–Wadsworth–Emmons olefination, offered in principle a very efficient procedure to obtain dienoate 13 (Scheme 3), and would leave only a single step in the synthesis of 2 [25]. Therefore, reagent 12 was prepared in two steps.…”

Section: Resultsmentioning

confidence: 99%

Asymmetric total synthesis of a putative sex pheromone component from the parasitoid wasp Trichogramma turkestanica

Geerdink¹,

Buter²,

Beek³

et al. 2014

Beilstein J. Org. Chem.

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SummaryVirgin females of the parasitoid wasp Trichogramma turkestanica produce minute amounts of a sex pheromone, the identity of which has not been fully established. The enantioselective synthesis of a putative component of this pheromone, (6S,8S,10S)-4,6,8,10-tetramethyltrideca-2E,4E-dien-1-ol (2), is reported as a contribution to this identification. Catalytic asymmetric conjugate addition of methylmagnesium bromide and stereoselective Horner–Wadsworth–Emmons olefinations are used as the key steps, and 2 was obtained in 16 steps with an overall yield of 4.4%.

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Synthesis of 4-Methyldienoates Using a Vinylogous Horner−Wadsworth−Emmons Reagent. Application to the Synthesis of Trichostatic Acid

Cited by 23 publications

References 50 publications

Sequence Matters: Modulating Electronic and Optical Properties of Conjugated Oligomers via Tailored Sequence

Sequence Matters: Modulating Electronic and Optical Properties of Conjugated Oligomers via Tailored Sequence

Regio- and stereospecific rhodium-catalyzed allylic alkylation with an acyl anion equivalent: an approach to acyclic α-ternary β,γ-unsaturated aryl ketones

Asymmetric total synthesis of a putative sex pheromone component from the parasitoid wasp Trichogramma turkestanica

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