Stereocontrolled total synthesis of (5Z,8Z11Z,13E)(15S)-15-hydroxyeicosa-5,8,11,13-tetraenoic acid (15S-HETE) and analogues

Nicolaou, K. C.; Ladduwahetty, T.; Elisseou, E. Michael

doi:10.1039/c39850001580

Cited by 16 publications

(18 citation statements)

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“…Although partial reduction using Ni(OAc) 2 , NaBH 4 , and ethylenediamine under a hydrogen atmosphere produced not only the desired compound but also its overreduced products, the hydrogenation of 14 using Lindlar's catalyst regioselectively provided the partial reduction product, and the subsequent removal of the silyl group under mild basic conditions successfully afforded the desired alkyne 3. 8 Scheme 4 shows the synthesis of natural RvE3 (17R,18R-diHEPE, 1a). An Evans aldol reaction with known oxazolidinone 15 6 and propanal (16) was carried out in the presence of n-Bu 2 BOTf and Et 2 NH to furnish the syn-aldol adduct 6 in high stereoselectivity (syn/anti = 98:2).…”

mentioning

confidence: 99%

Synthesis of Resolvin E3, a Proresolving Lipid Mediator, and Its Deoxy Derivatives: Identification of 18-Deoxy-resolvin E3 as a Potent Anti-Inflammatory Agent

et al. 2020

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We synthesized RvE3 and its deoxy derivatives, 17-deoxy-RvE3 and 18-deoxy-RvE3, by a common route via Sonogashira coupling as a key step. The evaluation of their anti-inflammatory activities revealed that 18-deoxy-RvE3 was remarkably more potent than the parent RvE3 and significantly active at a 300 fg dose in mice; additionally, 17-deoxy-RvE3 was significantly less potent than the parent RvE3. For the first time, we found that the 17-hydroxy group of RvE3 is very important for anti-inflammatory activity.

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confidence: 99%

Synthesis of Resolvin E3, a Proresolving Lipid Mediator, and Its Deoxy Derivatives: Identification of 18-Deoxy-resolvin E3 as a Potent Anti-Inflammatory Agent

et al. 2020

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“…The following compounds were prepared by literature methods: 6-chloro-9-tetrahydropyranyl-9H-purine, [13] 1a, [14] 8a, [15] 8b, [16] 8c, [17] 8d. [18] Cytokinin activity, [1,3] and inhibition of 15-LO [5] were determined as described before.…”

Section: Methodsmentioning

confidence: 99%

Synthesis of Optically Active 6‐Alkynyl‐ and 6‐Alkylpurines as Cytokinin Analogs and Inhibitors of 15‐Lipoxygenase; Studies of Intramolecular Cyclization of 6‐(Hydroxyalkyn‐1‐yl)purines

Berg¹,

Gundersen²,

Eriksen³

et al. 2005

Eur J Org Chem

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Optically active 6‐alkynyl‐ and 6‐alkylpurines have been synthesized. These compounds can be regarded as analogs of cytokinin plant growth hormones. The analogs were examined as growth stimulators and as inhibitors of 15‐lipoxygenase (15‐LO). The (S)‐enantiomer of 6‐(5‐hydroxy‐4‐methylpent‐1‐yl)purine exhibited profound growth stimulation activity, especially at low concentrations. 6‐(Hydroxyalkyn‐1‐yl)purines were found to cyclize by nucleophilic exo attack from the hydroxy group at the triple bond. (Z)‐Isomers were formed under acidic conditions. Plant growth stimulators and 15‐LO inhibitors were identified among the cyclization products. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)

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“…The alkenyl iodides employed as coupling partners in this study were prepared as shown in Scheme 3. Sequential treatment of 6-tert-butyldimethylsilyloxyhex-1-yne (13) 16 with methyllithium and iodine 17 in THF provided the iodo alkyne 14, which, upon reduction with diimine, 18 provid-ed the (Z)-iodo alkene 15 in an overall yield of 62% from 13. On the other hand, reaction of 13 with Schwartz's reagent 19 in dichloromethane, followed by treatment of the resultant intermediate with iodine, produced the (E)-iodo alkene 16 (74%).…”

Section: Methodsmentioning

confidence: 99%

“…A solution of MeLi (5.62 mmol) in Et 2 O (3.75 mL) was added to a cold (-78 ∞C), stirred solution of 6-(tert-butyldimethylsiloxy)hex-1-yne (13) 16 (1.09 g, 5.13 mmol) in anhyd Et 2 O (51 mL). The resulting mixture was stirred for 15 min.…”

Section: -(Tert-butyldimethylsiloxy)-1-iodohex-1-yne (14)mentioning

confidence: 99%

Conversion of Iodocyclopropanes into Cyclopropylzinc Chlorides and Pd(0)-Catalyzed Cross-Coupling of the Latter Derivatives with Alkenyl Iodides and Iodobenzene: Stereospecific Synthesis of 1,2-Bisalkenylcyclopropanes and 1-Alkenyl-2-phenylcyclopropanes

Piers

Coish

2001

Synthesis

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A method for the preparation of functionalized cyclopropylzinc chlorides, which involves treatment of substituted 2-alkenyl-1-iodocyclopropanes with BuLi followed by transmetalation of the resultant cyclopropyllithium with zinc chloride, is described. Palladium(0)-catalyzed cross-coupling of the cyclopropylzinc chloride derivatives with alkenyl iodides or iodobenzene provides highly substituted 1,2-bisalkenylcyclopropanes or 1-alkenyl-2-phenylcyclopropanes. In two of the cases studied, the initially formed cis-1,2-bisalkenylcyclopropanes 27, 29 underwent partial Cope rearrangement under the cross-coupling conditions to afford the corresponding 1,4-cycloheptadienes 28 and 30, respectively.A recent report 1 from this laboratory described an effective method for the preparation of functionalized, stereodefined iodocyclopropanes. These substances appear to be ideal substrates for the preparation of metallocyclopropanes, 2,3 which, in turn, could be employed as partners in transition metal-catalyzed cross-coupling reactions. It was therefore decided to investigate the Pd(0)-catalyzed cross-coupling of cyclopropylzinc compounds (derived from the corresponding iodocyclopropanes) with alkenyl and aryl iodides as a potential method for preparing highly substituted 1,2-bisalkenylcyclopropanes 4 and 1-aryl-2-alkenylcyclopropanes. The overall synthetic transformations, which are shown in general terms in Scheme 1, are both convergent and stereospecific. The first step of the sequence is a metal-halogen exchange reaction 5 in which the iodocyclopropane is treated with BuLi to provide the corresponding cyclopropyllithium A. Based on the pioneering studies of Walborsky et al., 6 A would be expected to be configurationally stable. The second step, a transmetalation reaction resulting from treatment of A with ZnCl 2 , would provide the cyclopropylzinc derivative B. To this point the sequence represents a novel method for the preparation of cyclopropylzinc reagents. In the final step of the sequence, the zinc derivative B would be coupled with an alkenyl or aryl iodide in the presence of a catalytic amount of (Ph 3 P) 4 Pd to provide a highly substituted, stereodefined 1,2-bisalkenylcyclopropane or a 2-alkenyl-1-arylcyclopropane.The preparation of substituted cyclopropanes via Negishitype couplings 7 of cyclopropylzinc reagents with alkenyl or aryl halides has been reported by our group 8 and, more recently, by others. 9 However, the generation of the requisite cyclopropylzinc species from iodocyclopropanes and subsequent Pd(0)-catalyzed coupling of the former intermediates with alkenyl iodides has not been extensively investigated. 10 In contrast, iodocyclopropanes have been employed directly as partners in cross-coupling reactions with metalloid reagents. Charette and coworkers have described Suzuki-type couplings of iodocyclopropanes with aryl-and alkenylboronic acids 11 and, more recently, with cyclopropylboronate esters. 12 In this paper, we report the use of iodocyclopropanes as precursors to cyclopropylzinc chlorides, which...

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Stereocontrolled total synthesis of (5Z,8Z11Z,13E)(15S)-15-hydroxyeicosa-5,8,11,13-tetraenoic acid (15S-HETE) and analogues

Abstract: A novel and stereoselective synthesis of 15s-HETE and a number of analogues based on a Cul-PdO coupling reaction is described.

Cited by 16 publications

References 1 publication

Synthesis of Resolvin E3, a Proresolving Lipid Mediator, and Its Deoxy Derivatives: Identification of 18-Deoxy-resolvin E3 as a Potent Anti-Inflammatory Agent

Synthesis of Resolvin E3, a Proresolving Lipid Mediator, and Its Deoxy Derivatives: Identification of 18-Deoxy-resolvin E3 as a Potent Anti-Inflammatory Agent

Synthesis of Optically Active 6‐Alkynyl‐ and 6‐Alkylpurines as Cytokinin Analogs and Inhibitors of 15‐Lipoxygenase; Studies of Intramolecular Cyclization of 6‐(Hydroxyalkyn‐1‐yl)purines

Conversion of Iodocyclopropanes into Cyclopropylzinc Chlorides and Pd(0)-Catalyzed Cross-Coupling of the Latter Derivatives with Alkenyl Iodides and Iodobenzene: Stereospecific Synthesis of 1,2-Bisalkenylcyclopropanes and 1-Alkenyl-2-phenylcyclopropanes

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