I. F. Dempsey Hyatt

Reactions of Hypervalent Iodonium Alkynyl Triflates with Azides: Generation of Cyanocarbenes

The creation of a fundamentally novel process can facilitate the development of shorter, and often more green, syntheses. Additionally, those novel processes which have the potential to reveal otherwise unimagined pathways to valuable reactive intermediates from simple, readily available substances warrant closer investigation. Towards these goals, we report herein a new method to generate cyanocarbene intermediates (2) from hypervalent iodonium alkynyl triflates (HIATs; 1) and azides, a reaction that converts an azide and two carbon atoms of an alkyne into dinitrogen and a cyanocarbene (Scheme 1). The value of this reactive intermediate, formed from readily available starting materials, is illustrated by three different carbene reactions including O H insertion, sulfoxide coordination, and cyclopropanation.

1,2,4-Triazine -picolinamide functionalized, nonadentate chelates for the segregation of lanthanides( iii ) and actinides( iii ) in biphasic systems

A novel family of nonadentate ligands based on the (5,6-diphenyl-1,2,4-triazin-3-yl)-picolinamide donor moiety has been synthesized from simple starting materials in high yield and purity. This group of ligands is an addition to the neutral nonadentate group but the first to incorporate 1,2,4-triazine. Their ability to extract a select group of lanthanides from acidic aqueous solution has been correlated to their ability to meet the ideal trigonal tricapped prismatic geometry that is seen by lanthanides and actinides in aqueous solution. The rate of metallation was determined using UV/VIS spectroscopy with pseudo first order conditions and showed similar behaviour to literature examples. Theoretical calculations were used to probe the bonding structure with lanthanides and actinides to predict the potential Ln/An segregating ability of the new ligands.

Sequential Pd(0)-, Rh(I)-, and Ru(II)-Catalyzed Reactions in a Nine-Step Synthesis of Clinprost

A step-economical synthesis of clinprost is reported that concludes with 3 different transition metal-catalyzed reactions: Pd-catalyzed decarboxylation with allylic rearrangement, Rh-catalyzed diene-ene [2+2+1] reaction, and Ru-catalyzed cross-metathesis reaction. The complexity bestowed to the molecule from these reactions converts a readily accessible ester to clinprost without using protecting groups in only 9 total steps.

Hypervalent iodine-guided electrophilic substitution: para-selective substitution across aryl iodonium compounds with benzyl groups

The reactivity of benzyl hypervalent iodine intermediates was explored in congruence with the reductive iodonio-Claisen rearrangement (RICR) to show that there may be an underlying mechanism which expands the reasoning behind the previously known C–C bond-forming reaction. By rationalizing the hypervalent iodine’s metal-like properties it was concluded that a transmetallation mechanism could be occurring with metalloid groups such as silicon and boron. Hypervalent iodine reagents such as Zefirov’s reagent, cyclic iodonium reagents, iodosobenzene/BF3, and PhI(OAc)2/BF3 or triflate-based activators were tested. A desirable facet of the reported reaction is that iodine(I) is incorporated into the product thus providing greater atom economy and a valuable functional group handle for further transformations. The altering of the RICR’s ortho-selectivity to form para-selective products with benzyl hypervalent iodine intermediates suggests a mechanism that involves hypervalent iodine-guided electrophilic substitution (HIGES).

Synthesis of hypervalent iodonium alkynyl triflates for the application of generating cyanocarbenes.

The procedures described in this article involve the synthesis and isolation of hypervalent iodonium alkynyl triflates (HIATs) and their subsequent reactions with azides to form cyanocarbene intermediates. The synthesis of hypervalent iodonium alkynyl triflates can be facile, but difficulties stem from their isolation and reactivity. In particular, the necessity to use filtration under inert atmosphere at -45 °C for some HIATs requires special care and equipment. Once isolated, the compounds can be stored and used in reactions with azides to form cyanocarbene intermediates. The evidence for cyanocarbene generation is shown by visible extrusion of dinitrogen as well as the characterization of products that occur from O-H insertion, sulfoxide complexation, and cyclopropanation. A side reaction of the cyanocarbene formation is the generation of a vinylidene-carbene and the conditions to control this process are discussed. There is also potential to form a hypervalent iodonium alkenyl triflate and the means of isolation and control of its generation are provided. The O-H insertion reaction involves using a HIAT, sodium azide or tetrabutylammonium azide, and methanol as solvent/substrate. The sulfoxide complexation reaction uses a HIAT, sodium azide or tetrabutylammonium azide, and dimethyl sulfoxide as solvent. The cyclopropanations can be performed with or without the use of solvent. The azide source must be tetrabutylammonium azide and the substrate shown is styrene.

Hypervalent Iodonium Alkynyl Triflate Generated Phenylcyanocarbene and Its Reactivity with Aromatic Systems

Phenylcyanocarbene was generated by the reaction of azide with a hypervalent iodonium alkynyl triflate and reacted in situ with 21 different carbocyclic and heterocyclic aromatic compounds. These reactions led to more complex products that frequently underwent subsequent rearrangements. The reactivity was further explored in a mechanistic study to ascertain the chemoselectivity and stereospecificity.

Decarboxylative and dehydrative coupling of dienoic acids and pentadienyl alcohols to form 1,3,6,8-tetraenes

Dienoic acids and pentadienyl alcohols are coupled in a decarboxylative and dehydrative manner at ambient temperature using Pd(0) catalysis to generate 1,3,6,8-tetraenes. Contrary to related decarboxylative coupling reactions, an anion-stabilizing group is not required adjacent to the carboxyl group. Of mechanistic importance, it appears that both the diene of the acid and the diene of the alcohol are required for this reaction. To further understand this reaction, substitutions at every unique position of both coupling partners was examined and two potential mechanisms are presented.