| 1. |
- Ahmad, Anees, et al.
(författare)
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Oxidative rearrangement of alkenes using in situ generated hypervalent iodine(III)
- 2013
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Ingår i: Tetrahedron Letters. - : Elsevier BV. - 0040-4039 .- 1359-8562. ; 54:43, s. 5818-5820
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Tidskriftsartikel (refereegranskat)abstract
- A novel protocol for the oxidative rearrangement of alkenes using in situ generated hypervalent iodine(III) was developed. This approach uses inexpensive, readily available, and stable chemicals (PhI, mCPBA, and TsOH) giving rearrangement products in yields comparable to those obtained using the more expensive commercially available [hydroxy(tosyloxy)iodo]benzene [HTIB or Koser's reagent]. Additionally, an alternative protocol for the synthesis of 1-methyl-2-tetralone through the one-step epoxidation/rearrangement of 4-methyl-1,2-dihydronaphthalene using mCPBA and TsOH was developed.
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| 2. |
- Ballantyne, Kaye N., et al.
(författare)
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Toward Male Individualization with Rapidly Mutating Y-Chromosomal Short Tandem Repeats
- 2014
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Ingår i: Human Mutation. - : John Wiley & Sons. - 1059-7794 .- 1098-1004. ; 35:8, s. 1021-1032
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Tidskriftsartikel (refereegranskat)abstract
- Relevant for various areas of human genetics, Y-chromosomal short tandem repeats (Y-STRs) are commonly used for testing close paternal relationships among individuals and populations, and for male lineage identification. However, even the widely used 17-loci Yfiler set cannot resolve individuals and populations completely. Here, 52 centers generated quality-controlled data of 13 rapidly mutating (RM) Y-STRs in 14,644 related and unrelated males from 111 worldwide populations. Strikingly, greater than99% of the 12,272 unrelated males were completely individualized. Haplotype diversity was extremely high (global: 0.9999985, regional: 0.99836-0.9999988). Haplotype sharing between populations was almost absent except for six (0.05%) of the 12,156 haplotypes. Haplotype sharing within populations was generally rare (0.8% nonunique haplotypes), significantly lower in urban (0.9%) than rural (2.1%) and highest in endogamous groups (14.3%). Analysis of molecular variance revealed 99.98% of variation within populations, 0.018% among populations within groups, and 0.002% among groups. Of the 2,372 newly and 156 previously typed male relative pairs, 29% were differentiated including 27% of the 2,378 father-son pairs. Relative to Yfiler, haplotype diversity was increased in 86% of the populations tested and overall male relative differentiation was raised by 23.5%. Our study demonstrates the value of RMY-STRs in identifying and separating unrelated and related males and provides a reference database.
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| 3. |
- Bielawski, Marcin, 1981-
(författare)
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Diaryliodonium Salts : Development of Synthetic Methodologies and α-Arylation of Enolates
- 2011
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- This thesis describes novel reaction protocols for the synthesis of diaryliodonium salts and also provides an insight to the mechanism of α-arylation of carbonyl compounds with diaryliodonium salts. The first chapter gives a general introduction to the field of hypervalent iodine chemistry, mainly focusing on recent developments and applications of diaryliodonium salts. Chapter two describes the synthesis of electron-rich to electron-poor diaryliodonium triflates, in moderate to excellent yields from a range of arenes and iodoarenes. In chapter three, it is described that molecular iodine can be used together with arenes in a direct one-pot, three-step synthesis of symmetric diaryliodonium triflates. A large scale synthesis of bis(4-tert-butylphenyl)iodonium triflate is also described, controlled and verified by an external research group, further demonstrating the reliability of this methodology. The fourth chapter describes the development of a sequential one-pot synthesis of diaryliodonium salts from aryl iodides and boronic acids, furnishing symmetric and unsymmetric, electron-rich to electron-poor diaryliodonium tetrafluoroborates in moderate to excellent yields. This method was developed to overcome the regiochemical limitations imposed by the reaction mechanism in the protocols described in the preceding chapters. Chapter five describes a one-pot synthesis of heteroaromatic iodonium salts under similar conditions described in chapter two. The final chapter describes the reaction of enolates with chiral diaryliodonium salts or together with a phase transfer catalyst yielding racemic products. DFT calculations were performed, which revealed a low lying energy transition state (TS) between intermediates, which is believed to be responsible for the lack of selectivity observed in the experimental work. It is also proposed that a [2,3] rearrangement is preferred over a [1,2] rearrangement in the α-arylation of carbonyl compounds. The synthetic methodology described in this thesis is the most generally applicable, efficient and high-yielding to date for the synthesis of diaryliodonium salts, making these reagents readily available for various applications in synthesis.
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| 4. |
- Bielawski, Marcin, et al.
(författare)
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One-Pot Synthesis and Applications of N-Heteroaryl Iodonium Salts
- 2014
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Ingår i: ChemistryOpen. - : Wiley. - 2191-1363. ; 3:1, s. 19-22
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Tidskriftsartikel (refereegranskat)abstract
- An efficient one-pot synthesis of N-heteroaryl iodonium triflates from the corresponding N-heteroaryl iodide and arene has been developed. The reaction conditions resemble our previous one-pot syntheses, with suitable modifications to allow N-heteroaryl groups. The reaction time is only 30min, and no anion exchange is required. The obtained iodonium salts were isolated in a protonated form, these salts can either be employed directly in applications or be deprotonated prior to use. The aryl groups were chosen to induce chemoselective transfer of the heteroaryl moiety to various nucleophiles. The reactivity and chemoselectivity of these iodonium salts were demonstrated by selectively introducing a pyridyl moiety onto both oxygen and carbon nucleophiles in good yields.
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| 5. |
- Bouma, M. J., et al.
(författare)
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7.07 α-Oxygenation of Carbonyl Compounds
- 2014. - 2nd
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Ingår i: Comprehensive Organic Synthesis II (Second Edition). - Amsterdam : Oxford: Elsevier. - 9780080977430 ; , s. 213-241
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Bokkapitel (refereegranskat)abstract
- Abstract The chapter describes synthetically useful strategies for α-oxygenation of carbonyl compounds, with special emphasis on recent methods for catalytic and asymmetric reactions. The oxidation of enolates, enols, enol ethers, and α,β-unsaturated compounds is discussed in detail. Classical oxidation reagents like metal oxides, molecular oxygen, peroxides, and peracids are covered, with asymmetric dihydroxylation of enol ethers giving the highest enantioselectivities together with organocatalytic methods using peroxides. Oxaziridines, nitrosoarenes, and hypervalent iodine compounds are more recently developed α-oxygenation alternatives that allow metal-free oxidations under mild conditions. The combination of nitrosoarenes with organocatalysis is currently the best method for enantioselective α-oxygenations. The area of asymmetric α-oxygenations with hypervalent iodine compounds is currently under development, and high enantioselectivities have only been achieved in intramolecular reactions and epoxidations.
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| 6. |
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| 7. |
- Destouni, Georgia, et al.
(författare)
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Biogeochemical Transformation Pathways through the Land-water Geosphere
- 2014
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Konferensbidrag (refereegranskat)abstract
- Water on land undergoes and participates in many biogeochemical exchanges and changes. A bits-and-pieces approach to these may miss essential aspects of change propagation and transformation by land-water through different segments of the Earth system. This paper proposes a conceptualization of the entire land-water geosphere as a scale-free catchment-wise organised system (Figure 1), emphasizing four key new system aspects compared to traditional hydrosphere/water cycle view: i) distinction of coastal divergent in addition to traditional convergent catchments; ii) physical and social-ecological system coupling through four main nodal zones/interfaces (surface, subsurface, coastal, observation); iii) flow-transport pathways as system coupling agents; iv) multiple interactions with the anthroposphere as integral system parts. Utilizing this conceptualization, we identify distinct patterns of direct anthropogenic change in large-scale water and waterborne nutrient fluxes, emerging across different parts of the world. In general, its embedment directly in the anthroposphere/technosphere makes land-water a key geosphere for understanding and monitoring human-driven biogeochemical changes. Further progress in system-level understanding of such changes requires studies of land-water as a continuous yet structured geosphere following the proposed spatiotemporal pathways of change propagation-transformation.
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| 8. |
- Ghosh, Raju, et al.
(författare)
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Metal-Free One-Pot Synthesis of Benzofurans
- 2014
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Ingår i: Chemistry - A European Journal. - : Wiley. - 0947-6539 .- 1521-3765. ; 20:29, s. 8888-8892
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Tidskriftsartikel (refereegranskat)abstract
- Ethyl acetohydroxamate was efficiently arylated with diaryliodonium salts at room temperature under transition-metal-free conditions. The obtained O-arylated products were reacted in situ with ketones under acidic conditions to yield substituted benzo[b]furans through oxime formation, [3,3]-rearrangement, and cyclization in a fast and operationally simple one-pot fashion without using excess reagents. Alternatively, the O-arylated products could be isolated or transformed in situ to aryloxyamines or O-arylaldoximes. The methodology was applied to the synthesis of Stemofuran A and the formal syntheses of Coumestan, Eupomatenoid 6, and (+)-machaeriol B.
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| 9. |
- Ghosh, Raju, et al.
(författare)
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Metal-Free Synthesis of N-Aryloxyimides and Aryloxyamines
- 2014
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Ingår i: Organic Letters. - : American Chemical Society (ACS). - 1523-7060 .- 1523-7052. ; 16:6, s. 1830-1832
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Tidskriftsartikel (refereegranskat)abstract
- N-Hydroxyphthalimide and N-hydroxysuccinimide have been arylated with diaryliodonium salts to provide N-aryloxyimides in excellent yields in short reaction times. A novel hydrolysis under mild and hydrazine-free conditions yielded aryloxyamines, which are valuable building blocks in the synthesis of oxime ethers and benzofurans.
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| 10. |
- Ghosh, Raju, et al.
(författare)
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Room Temperature, Metal-Free Arylation of Aliphatic Alcohols
- 2014
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Ingår i: ChemistryOpen. - : Wiley. - 2191-1363. ; 3:2, s. 54-57
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Tidskriftsartikel (refereegranskat)abstract
- Diaryliodonium salts are demonstrated as efficient arylating agents of aliphatic alcohols under metal-free conditions. The reaction proceeds at room temperature within 90min to give alkyl aryl ethers in good to excellent yields. Aryl groups with electron-withdrawing substituents are transferred most efficiently, and unsymmetric iodonium salts give chemoselective arylations. The methodology has been applied to the formal synthesis of butoxycaine.
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