- Domino Aryne Annulation via a Nucleophilic-Ene Process
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1,2-Benzdiyne equivalents possess the unique property that they can react with two arynophiles through iteratively generated 1,2- and 2,3-aryne intermediates. Upon rational modification on the second leaving group of these aryne precursors, a domino aryne annulation approach was developed through a nucleophilic-ene reaction sequence. Various benzo-fused N-heterocyclic frameworks were achievable under transition metal-free conditions with a broad substrate scope.
- Xu, Hai,He, Jia,Shi, Jiarong,Tan, Liang,Qiu, Dachuan,Luo, Xiaohua,Li, Yang
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supporting information
p. 3555 - 3559
(2018/03/21)
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- Direct Cross-Coupling of Allylic C(sp3)?H Bonds with Aryl- and Vinylbromides by Combined Nickel and Visible-Light Catalysis
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An efficient protocol for the direct allylic C(sp3)?H bond activation of unactivated tri- and tetrasubstituted alkenes and their functionalization with aryl- and vinylbromides by nickel and visible-light photocatalysis has been developed. The method allows C(sp2)?C(sp3) formation under mild reaction conditions with good functional-group tolerance and excellent regioselectivity.
- Huang, Long,Rueping, Magnus
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supporting information
p. 10333 - 10337
(2018/07/31)
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- A Versatile Route to Unstable Diazo Compounds via Oxadiazolines and their Use in Aryl–Alkyl Cross-Coupling Reactions
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Coupling of readily available boronic acids and diazo compounds has emerged recently as a powerful metal-free carbon–carbon bond forming method. However, the difficulty in forming the unstable diazo compound partner in a mild fashion has hitherto limited their general use and the scope of the transformation. Here, we report the application of oxadiazolines as precursors for the generation of an unstable family of diazo compounds using flow UV photolysis and their first use in divergent protodeboronative and oxidative C(sp2)?C(sp3) cross-coupling processes, with excellent functional-group tolerance.
- Greb, Andreas,Poh, Jian-Siang,Greed, Stephanie,Battilocchio, Claudio,Pasau, Patrick,Blakemore, David C.,Ley, Steven V.
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supporting information
p. 16602 - 16605
(2017/12/13)
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- METHODS AND DEVICES FOR USING ISOPERILLYL ALCOHOL
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The present invention provides for a method of treating a disease such as cancer, comprising the step of administering to a patient a therapeutically effective amount of an isomer or analog of monoterpene or sesquiterpene (or its derivative), such as an i
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Page/Page column 35-36
(2012/06/30)
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- N-SUBSTITUTED PHENYLACETAMIDE DERIVATIVE AND PHARMACEUTICAL COMPOSITION COMPRISING THE SAME
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A compound represented by the formula: (I) wherein R1 represents a methoxy group, a hydroxyl group or a hydrogen atom; R2 represents a hydrogen atom, a C1-4 alkyl group, a C1-4 alkylcarbonyl group or an arylcarbonyl group; and D represents a group represented by the formula (A), (B) or (C) below. (A) (B) (C) This compound is useful as a therapeutic agent for a pain or inflammation induced by any one of various morbid conditions such as neuropathic pain, rheumatoid arthritis and osteoarthritis.
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Page/Page column 101-102
(2008/06/13)
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- 3,5-Bis(trifluoromethyl)phenyl sulfones in the Julia-Kocienski olefination - Application to the synthesis of tri- and tetrasubstituted olefins
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3,5-Bis(trifluoromethyl)phenyl (BTFP) sulfones 8a-d are successfully employed in the modified Julia olefination reaction with carbonyl compounds employing phosphazene base P4-tBu at room temp. in THF, affording tri- and tetrasubstituted olefins in good yi
- Alonso, Diego A.,Fuensanta, Monica,Najera, Carmen
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p. 4747 - 4754
(2007/10/03)
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- Highly diastereoselective formation of spirocyclic compounds via 1,5-hydrogen transfer: A total synthesis of (-)-erythrodiene
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(Chemical Equation Presented) A highly stereoselective synthesis of (-)-erythrodiene starting from 4-isopropylcyclohexanone is described. The key reactions are an asymmetric methoxycarbonylation of the starting ketone and a highly diastereoselective radical cascade involving addition of a phenylthiyl radical to a terminal alkyne followed by a 1,5-hydrogen transfer and a 5-exo-cyclization.
- Lachia, Mathilde,Denes, Fabrice,Beaufils, Florent,Renaud, Philippe
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p. 4103 - 4106
(2007/10/03)
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- Enantioselective synthesis of (+)-α-vetivone through the Michael reaction of chiral imines
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(+)-α-Vetivone has been synthesised in nine steps. The absolute stereochemistry of the two stereogenic centres is controlled in the same key step involving the stereoselective Michael addition of a chiral imine of 4-isopropylidene-2-methylcyclohexanone to phenyl crotonate.
- Revial, Gilbert,Jabin, Ivan,Pfau, Michel
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p. 4975 - 4983
(2007/10/03)
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- Halogenated Terpenoids. XXIX the 1-Bromo 1-Bromomethyl Cyclohexyl System
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Bromination of methylene groups exocyclic to cyclohexyl systems normally affords two isomeric products; the axial 1-bromo equatorial 1-bromomethyl compound and the axial 1-bromomethyl equatorial 1-bromo derivative. Free energy differences between these two isomers, and the conformations adopted by the axial 1-bromomethyl group, have been explored by n.m.r. spectroscopy, by X-ray crystallography and by MM3 calculations. Evidence is presented to show that the ax-bromomethyl group exists primarily as those rotamers which site the bromine atom synclinal to the vicinal bromine. The A value for a bromomethyl group in this system is then similar to that of an unsubstituted methyl group.
- Brecknell, Douglas J.,Carman, Raymond M.,Edwards, Ross A.,Hansford, Karl A.,Karoli, Tomislav,Robinson, Ward T.
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p. 689 - 700
(2007/10/03)
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- The Interaction of π orbitals with a carbocation over three σ bonds
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The semi-π analogue of double hyperconjugation ("hyperconjugation/conjugation") has been examined in 4-isopropylidenecyclohexyl mesylate (4-OMs) by comparison with the saturated analogue, trans-4-isopropylcyclohexyl mesylate (5-OMs). The unsaturated substrate reacts in 97% trifluoroethanol only four times faster than the saturated substrate. Raber-Harris plots indicate that both substrates react by ks mechanisms; i.e., solvolysis occurs with solvent assistance rather than carbocation formation. These results are consistent with the absence of a direct, through-bond interaction of the double bond with the reactive center. The absence is caused at least in part by less than ideal overlap of the γ,δ π orbitals with the α,β σ orbitals. In contrast, an electron-rich tin atom attached to the 4-position provides a large rate enhancement and changes the mechanism to carbocation formation through double hyperconjugation.
- Lambert, Joseph B.,Ciro, Sol M.
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p. 1940 - 1945
(2007/10/03)
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