Flow synthesis of iodonium trifluoroacetates through direct oxidation of iodoarenes by Oxone®

Flow chemistry is considered to be a versatile and complementary methodology for the preparation of valuable organic compounds. We describe a straightforward approach for the synthesis of iodonium trifluoroacetates through the direct oxidation of iodoarenes in a simple flow reactor using an Oxone‐filled cartridge. Optimization has been carried out using the Nelder–Mead algorithm. The procedure allows a wide range of iodonium salts to be prepared from simple starting materials

Enantio‐ and Diastereoselective Cyclopropanation of 1‐Alkenylboronates : Synthesis of 1‐Boryl‐2,3‐Disubstituted Cyclopropanes

A novel, highly enantio- and diastereoselective synthesis of 1-boryl-2,3-disubstituted cyclopropanes has been developed by means of the cyclopropanation of alkenylboronates with ethyl diazoacetate in the presence of catalytic amounts of a chiral copper(I) complex. The products can also be directly accessed from alkynes through an operationally simple, sequential hydroboration–cyclopropanation protocol. The resulting enantioenriched 1-boryl-2,3-disubstituted cyclopropanes are versatile synthetic intermediates that undergo further transformations at the carbon–boron bond.We thank MINECO for financial support (CTQ2014-52769- C03-01-R and Juan de la Cierva fellow for J.C.) and Junta de Andaluc a (P12-FQM-1765). We also thank Riccardo Gava and Cristina Gonzalez for additional experiments and Francisco Molina for X-ray diffraction studies

Applications of Hypervalent Iodine Reagents: From Enantioselective Copper-Catalysed Arylation-Semipinacol Cascade to Methionine Functionalisation for Peptide Macrocyclisation

The unifying theme of this thesis is the exploitation of the reactivity of aryliodonium salts as electrophile transfer reagents. In the first part of the thesis, diaryliodonium salts are employed as arylation reagents for the enantioselective copper-catalysed arylative semipinacol rearrangement (SPR) of various tertiary allylic alcohols. This cascade reaction is a rare example of asymmetrically activating SPR using carbon electrophiles. Different substrate classes – including dihydropyran, indene and dihydronaphthalene moieties – are converted to enantioenriched beta-aryl spirocyclic ketones in excellent yields and enantioselectivities, and often as a single diastereomer. These are in turn useful functional handles for transformations into other moieties, including further rearrangements via Baeyer-Villiger oxidation. In the second part of this thesis, a two-step process for the macrocyclisation of native peptides via a non-natural linkage is developed. This study exploits previous work conducted in the group on the use of aryliodonium salts as methionine-selective diazoacetate transfer reagents. The functionalised methionine is in turn used for an intramolecular rhodium-catalysed insertion into tryptophan. Eventual translation onto solid-phase enables facile access into various macrocyclic peptides.Agency for Science, Technology and Research (A*STAR), SIngapore (PhD scholarship, D.H.L.) EPSRC (EP/100548X/1), ERC (ERC-STG-259711), (M.J.G.) Royal Society (Wolfson Merit Award) for supporting this research (M.J.G.

Enantioselective Copper-Catalyzed Arylation-driven Semi-Pinacol Rearrangement of Allylic Alcohols with Diaryliodonium Salts

A copper-catalyzed enantioselective arylative semi-pinacol rearrangement of allylic alcohols using diaryliodonium salts is reported. Chiral Cu(II)-bisoxazoline catalysts initiate an electrophilic alkene arylation, triggering a 1,2-alkyl migration to afford a range of non-racemic spirocyclic ketones with high yields, diastero- and enantioselectivities.Gaunt MJ: EPSRC (EP/100548X/1), ERC (ERC-STG-259711), and Royal Society (Wolfson Award). Lukamto DH: Agency for Science Technology and Research (A*STAR, Singapore) for PhD scholarship

The Effects of Marcus' materialistic life style on his children and grandchildren in Helman's The Little Foxes and Another Part of The Forest

In this thesis, I discuss the materialistic life style of the Hubbard families. I want to reveal Marcus? materialistic life style as the father or the leader in the Hubbard family and the effects of his materialistic life style on his children and grandchildren. To get criticisms and information about the effects of Marcus? materialistic life style I use library and internet researches. Hellman?s plays The Little Foxes and Another Part of the Forest are the primary data. In my analysis I use literary approach and employ the literary tools of characterization and conflict. I also need the concept of materialistic life style to support my analysis. This play talks about the Hubbards who at last have the same life style as Marcus. The characters discussed here are Marcus (the father), Ben, Oscar, Regina (the children), Leo and Alexandra (the grandchildren). The children were not born to have materialistic life style but are taught by their father in their daily life. As my findings, I prove that the life style of the father is inherited by their children, and transmitted to their grandchildren. They live for money and do not have love. However, one person, Alexandra does not become like the other members of the family because she learns that living like them will result in the same tragedy and even more

Enantioselective Copper-Catalyzed Arylation-driven Semi-Pinacol Rearrangement of Allylic Alcohols with Diaryliodonium Salts

A copper-catalyzed enantioselective arylative semi-pinacol rearrangement of allylic alcohols using diaryliodonium salts is reported. Chiral Cu(II)-bisoxazoline catalysts initiate an electrophilic alkene arylation, triggering a 1,2-alkyl migration to afford a range of non-racemic spirocyclic ketones with high yields, diastero- and enantioselectivities.Gaunt MJ: EPSRC (EP/100548X/1), ERC (ERC-STG-259711), and Royal Society (Wolfson Award). Lukamto DH: Agency for Science Technology and Research (A*STAR, Singapore) for PhD scholarship

The Election Online: Debate, Support, Community

This book provides a comprehensive analysis of the 2016 Australian federal election