Applications of the stereochemically-controlled Horner-Wittig reaction: synthesis of feniculin, (E)-non-6-en-1-ol, a pheromone of the mediterranean fruit fly, (E)- and (Z)-dec-5-en-1-ol, tri-substituted alkenes, and (Z)-α-bisabolene

Buss, Antony D.; Greeves, Nick; Mason, Ralph P.; Warren, Stuart

doi:10.1039/p19870002569

Cited by 36 publications

(13 citation statements)

References 12 publications

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“…Starting materials: The following starting materials were prepared according to literature procedures: ethyl a-(bromomethyl)acrylate, [17] 1-phenylcyclopent-1-ene (5 b), [18] 1-methyl-3H-indene (5 c), [19] 3,4-dihydro-1-methylnaphthalene (5 d), [19] E-2-phenylbut-2-ene (E-9), [20] Z-2-phenylbut-2-ene (Z-9), [20] E-2-(2-p-anisyl)-but-2-ene (E-10), [21] Z-2-(2-p-anisyl)-but-2-ene (Z-10), [21] E-3-methyl-5-phenylpent-2-ene (E-12), [22] Z-3-methyl-5-phenylpent-2-ene (Z-12). [22] Preparation of the starting materials Diisopropylzinc: A 1.3m solution of isopropylmagnesium bromide in diethyl ether was prepared from 2-bromopropane (38.8 g, 0.32 mol) and magnesium (8.5 g, 0.35 mol) and transferred by cannula to a 500 mL 2-necked flask.…”

Section: Methodsmentioning

confidence: 99%

“…[22] Preparation of the starting materials Diisopropylzinc: A 1.3m solution of isopropylmagnesium bromide in diethyl ether was prepared from 2-bromopropane (38.8 g, 0.32 mol) and magnesium (8.5 g, 0.35 mol) and transferred by cannula to a 500 mL 2-necked flask. Zinc bromide (35.5 g, 0.16 mol) was dried (120 8C, 1 mmHg, 2 h) and dissolved in diethyl ether (150 mL, ca.…”

Section: Methodsmentioning

confidence: 99%

“…The two isomers were unequivocally asigned by NOESY-experiments. 3, 132.4, 130.3, 124.9, 122.9, 131.3, 57.8, 26.9, 17.2; MS (EI): m/z (%): 162 (100) [M ], 147 (28), 131 (22), 105 (22) Z-and E-1-methoxy-4-(1-methyl-1-propenyl)benzene (10): Following the same procedure as above, the crude product (33.0 g; 74 %) was obtained from 4-methoxyacetophenone (40.4 g). Distillation over a spinning band column afforded the Z isomer (6 g; Z:E 98:2) at b.p.…”

Section: Methodsmentioning

confidence: 99%

“…The crude product was purified by flash-chromatography (hexanes). 7.15 (m,4 H),6.00 ± 5.86 (m,1 H),5.17 ± 5.06 (m,2 H),3.08 (dd,J 15.8 Hz,J 7.8 Hz,1 H) 6,137.5,126.2 (2C),124.4,123.2,115.5,48.4,44.74,38.4,37.7,18.5;cis product: 149.2,142.3,138.0,126.2 (2C),124.4,123.5,115.3,43.0,41.7,36.5,34.4,15.2;MS (EI): m/z (%): 172 (2) [M ], 143 (17), 131 (23), 130 (100), 129 (25), 115 (22), 91 (16); elemental analysis (%) calcd for C 13 H 16 (172.27 5, 137.2, 128.3, 128.3, 127.6 (2C), 125.9, 115.5, 50.4, 43.2, 38.7, 36.1, 32.0, 26.9, 26.5 3,146.1,139.4,128.2,127.7,125.9,125.8,60.3,51.4,40.8,37.4,36.2,31.8,27.0,26.2,14.1;MS (EI): m/z (%): 272 …”

Section: Methodsmentioning

confidence: 99%

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Stereoselective Preparation and Reactions of Configurationally Defined Dialkylzinc Compounds

Boudier¹,

Darcel²,

Flachsmann³

et al. 2000

Chem. Eur. J.

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The reaction of cyclic and open-chain diastereomerically pure secondary organoboranes with diisopropylzinc allows the preparation of secondary dialkylzinc reagents with good to excellent retention of configuration as shown by deuterolysis and CuI- and Pd0-mediated reactions with electrophiles. The importance of a high boron-zinc exchange rate to obtain high diastereoselectivity has been shown. Improvement of the configurational stability and stereomeric purity of the zinc intermediates has been obtained by using mono-isopinocampheylborane ((-)-IpcBH2) providing optically active dialkylzinc compounds (up to 96% ee) with enhanced diastereoselectivities.

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Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

See 2 more Smart Citations

Stereoselective Preparation and Reactions of Configurationally Defined Dialkylzinc Compounds

Boudier¹,

Darcel²,

Flachsmann³

et al. 2000

Chem. Eur. J.

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“…The enols are diversely represented amongst physiologically active compounds (1)(2)(3)(4)(5)(6)(7)(8). Many important pheromones of the sex attractant (2-4) and the insect feedant types (1) possess enolic functions.…”

Section: Introductionmentioning

confidence: 99%

The identification of structural fragments of enolic monoterpenes, enolic pheromones, and related natural products, from OH stretching vibration frequencies and relative intensities

Bacon¹,

Maas²

1989

Can. J. Chem.

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Can. J. Chem. 67, 250 (1989). The OH stretching frequency has proved to be a powerful tool for structural investigations of enolic natural products containing diverse structural elements. The position of unsaturation can in many cases be determined directly from frequency measurements. Primary, secondary, and tertiary a-p and P-y unsaturation can unambiguously be identified due to the possession of OH bands arising from an interaction of the OH proton with the .rr system. Frequently, unsaturation further removed than the y position can be identified, particularly when a double bond is present, intermediate between the distal .rr system and the OH group. The identification of long-range OH-.rr system interactions relies on the observation that an intermediate double bond reduces the rotational freedom of the molecule. This reduction in entropy is assumed to be responsible for a significant population of the conformation in which the OH group is associated with the .rr system.Key words: infrared, conformation, natural products, alcohols, molecular structure. 250 (1989). La frequence de la vibration dlClongation OH s'avkre un outil puissant dans les etudes de structures des produits naturels tnoliques comportant divers elements de structure. Dans plusieurs cas, les mesures de frkquence permettent de determiner directement la position de l'insaturation. En se basant sur la presence de bandes OH provenant d'une interaction entre le proton du OH et le systkme .rr, on peut identifier sans ambigui'tks les insaturations a-p ainsi que P-y, tant primaire que secondaire ou tertiaire. On peut friquemment identifier des insaturations dont la position est plus tloignte que la position y ; cette affirmation est particulikrement vraie lorsqu'il existe une double liaison entre le systkme .rr tloigni et le groupement OH. L'identification des interactions OH-.rr B distance est bake sur l'observation qu'une double liaison intermediaire rtduit la liberte de rotation de la molCcule. On fait l'hypothkse que cette reduction de I'entropie est responsable de la presence d'une population importante de la conformation dans laquelle le groupement OH est associC avec le systkrne .rr.

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Stereoselective Michael Additions of Phosphorylated Allyl Carbanions − Synthesis of Functionalized Cyclopentylphosphonates and Phosphane Oxides

Ruan

Häßner

2001

Eur. J. Org. Chem.

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Keywords: Methylenecyclopentanes / [3ϩ2] Michael-induced ring closure / Phosphane oxides / Phosphonates / Stereoselectivity Dimethyl (2-chloromethyl-2-propenyl)phosphonate (3b) and (tert-butyl)[2-(chloromethyl)-2-propenyl](phenyl)phosphane oxide (3d) were prepared and their reactions with α,β-unsaturated esters 5a−c and ketone 5d, acting as phosphorylated trimethylenemethane equivalents by a [3+2] strategy, were investigated. With the use of LDA in the presence of DMPU, the Michael addition proceeded with high stereoselectivity and regioselectivity to afford methylenecyclopentyl-substituted dimethyl phosphonate or (tert-butyl)(phenyl)phosphane oxide derivatives 6a−d and 14(S P ). Compound 3d re-

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Applications of the stereochemically-controlled Horner-Wittig reaction: synthesis of feniculin, (E)-non-6-en-1-ol, a pheromone of the mediterranean fruit fly, (E)- and (Z)-dec-5-en-1-ol, tri-substituted alkenes, and (Z)-α-bisabolene

Cited by 36 publications

References 12 publications

Stereoselective Preparation and Reactions of Configurationally Defined Dialkylzinc Compounds

Stereoselective Preparation and Reactions of Configurationally Defined Dialkylzinc Compounds

The identification of structural fragments of enolic monoterpenes, enolic pheromones, and related natural products, from OH stretching vibration frequencies and relative intensities

Stereoselective Michael Additions of Phosphorylated Allyl Carbanions − Synthesis of Functionalized Cyclopentylphosphonates and Phosphane Oxides

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