Allenyl allylic ethers: synthesis and thermal rearrangements

Dulcere, Jean Pierre; Crandall, Jack K.; Faure, Robert; Santelli, Maurice; Agati, V.; Mihoubi, M. N.

doi:10.1021/jo00073a032

Cited by 30 publications

(17 citation statements)

References 1 publication

(1 reference statement)

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“…Under similar conditions, the reaction of carene (1a) with PhICl 2 /I 2 resulted in a selective formation of a single diastereomer (3a) isolated in 90% yield after column chromatography on silica gel (Scheme 1). The formation of single diastereomers (2a) and (3a) due to the Markovnikov-type anti-addition of the electrophilic reagent from the less sterically hindered side of the double bond in (1a) is in agreement with the typical reactivity of (+)-3-carene (for example, see bromoallenyloxylation of (+)-3-carene 8 ). The structure of products (2a) and (3a) was assigned based on high resolution NMR and HRMS.…”

Section: Resultssupporting

confidence: 72%

Halomethoxylation of monoterpenes using (dichloroiodo)benzene

Yusubov¹,

Drygunova²,

Ткачев³

et al. 2005

Arkivoc

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Reactions of (dichloroiodo)benzene or (dichloroiodo)benzene/iodine with various monoterpenes in methanol provide a selective approach to the respective products of chloromethoxylation or iodomethoxylation of the double bond. The halomethoxylation of (+)-3-carene, carvone, and β-pinene proceeds with especially high regio-and stereoselectivity affording an appropriate single product in each case, while the reaction of limonene gives products of functionalization of both double bonds. This new methodology for the controlled introduction of halogen substituents into the structure of naturally occuring monoterpenes provides an entry into various potentially important synthetic intermediates.

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Section: Resultssupporting

confidence: 72%

Halomethoxylation of monoterpenes using (dichloroiodo)benzene

Yusubov¹,

Drygunova²,

Ткачев³

et al. 2005

Arkivoc

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“…Regioselective introduction of a substituent at the C3 position in monocyclic five-membered heterocycles has attracted longstanding interest, but it is far less common than the C2 substitution reactions. , Dihydrofurans are attractive synthetic targets, since they are subunits of a wide range of biologically active compounds. − However, existing approaches for the C3-substituted 2,3-dihydrofurans are extremely limited. Reliable protocols involve internal cyclization of 4-hydroxybutanal followed by dehydration (Scheme a) and rearrangements of 2-allenyloxy and 2-vinyloxy groups in 2,5-dihydrofuran (Scheme b,c), but their scope is somewhat limited.…”

mentioning

confidence: 99%

Ru(0)-Catalyzed C3-Selective Cross-Dimerization of 2,5-Dihydrofuran with Conjugated Dienes

et al. 2016

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Cross-dimerization of 2,5-dihydrofuran with conjugated dienes enables a straightforward and efficient synthesis of C3-substituted 2,3-dihydrofurans. The reaction has been achieved by Ru(η6-naphthalene)(η4-1,5-COD) (1) (3–10 mol %) in acetone at room temperature. This protocol is also effective for branched and linear internal conjugated dienes. The stereochemistry of the products suggests that the reaction involves the oxidative coupling step between cisoid-1,3-dienes and 2,5-dihydrofuran at a Ru(0) center.

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“…As shown in Scheme 2, reaction of dihydropyran 12 with propargyl alcohol in the presence of N -bromosuccinimide (NBS) at -20 °C for 2 h and then at 23 °C for 15 h furnished bromo ether 13 in 98% yield. 46 Bromo ether 13 was treated with DBU and the resulting mixture was heated at 110 °C for 5 h to provide the dehydrobromination product 14 in 85% yield. Enyne 14 was subjected to Pauson-Khand reaction with Co 2 (CO) 8 and NMO as described above to furnish tricyclic enone 15 in 20% yield.…”

Section: Resultsmentioning

confidence: 99%

Design and Synthesis of Highly Potent HIV-1 Protease Inhibitors Containing Tricyclic Fused Ring Systems as Novel P2 Ligands: Structure–Activity Studies, Biological and X-ray Structural Analysis

et al. 2018

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The design, synthesis, and biological evaluation of a new class of HIV-1 protease inhibitors containing stereochemically defined fused tricyclic polyethers as the P2 ligands and a variety of sulfonamide derivatives as the P2′ ligands, are described. A number of ring sizes and various substituent effects were investigated to enhance the ligand-backbone interactions in the protease active site. Inhibitors 5c and 5d containing this unprecedented fused 6-5-5 ring system as the P2 ligand, an aminobenzothiazole as the P2′ ligand and a difluorophenylmethyl as the P1 ligand exhibited exceptional enzyme inhibitory potency and maintained excellent antiviral activity against a panel of highly multidrug-resistant HIV-1 variants. The umbrella-like P2 ligand for these inhibitors has been synthesized efficiently in an optically active form using a Pauson-Khand cyclization reaction as the key step. The racemic alcohols were resolved efficiently using a lipase catalyzed enzymatic resolution. Two high resolution X-ray structures of inhibitor-bound HIV-1 protease revealed extensive interactions with the backbone atoms of HIV-1 protease and provided molecular insight into the binding properties of these new inhibitors.

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Allenyl allylic ethers: synthesis and thermal rearrangements

Cited by 30 publications

References 1 publication

Halomethoxylation of monoterpenes using (dichloroiodo)benzene

Halomethoxylation of monoterpenes using (dichloroiodo)benzene

Ru(0)-Catalyzed C3-Selective Cross-Dimerization of 2,5-Dihydrofuran with Conjugated Dienes

Design and Synthesis of Highly Potent HIV-1 Protease Inhibitors Containing Tricyclic Fused Ring Systems as Novel P2 Ligands: Structure–Activity Studies, Biological and X-ray Structural Analysis

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