Gas‐Phase Generation and Decomposition of a Sulfinylnitrene into the Iminyl Radical OSN

The dipolar oxathiazyne‐like sulfinylnitrene RS(O)N, a highly reactive α‐oxo nitrene, has been rarely investigated. Upon flash vacuum pyrolysis of sulfinyl azide CF₃S(O)N₃ at 350 °C, an elusive sulfinylnitrene CF₃S(O)N was generated in the gas phase in its singlet ground state and was characterized by matrix‐isolation IR spectroscopy. Further fragmentation of CF₃S(O)N at 600 °C produced CF₃ and a novel iminyl radical OSN, an SO₂ analogue, which were unambiguously identified by IR spectroscopy. Consistent with the experimental observations, DFT calculations clearly support a stepwise decomposition mechanism of CF₃S(O)N₃.     

The missing link: triplet fluorocarbonyl nitrene FC(O)N

The elusive triplet fluorocarbonyl nitrene, FC(O)N (X³A′′), has been generated in high yield from matrix‐isolated FC(O)N₃ by ArF excimer laser photolysis (λ=193 nm). As a side product FNCO was formed. The novel nitrene was characterized by IR, UV/Vis, EPR spectroscopy, and quantum‐chemical calculations. All six fundamental vibrations of FC(O)N at 1681.3, 1193.8, 879.8, 646.5, 588.7, and 434.8 cm^?1 (argon matrix, 16 K), their ^12/13C, ^16/18O, and ^14/15N isotopic shifts, and four electronic transitions at T₀=13 890, 25 428, 29 166, and 30 900 cm^?1 that exhibit vibrational fine structures have been detected. Under visible‐light irradiation at λ≥495 nm, FC(O)N reacted with molecular N₂ in the matrix cage at 6 K to give back FC(O)N₃, whereas near‐UV irradiation at λ≥335 nm yielded FNCO. The singlet–triplet energy gaps of different carbonyl nitrenes are discussed.     

Heterocumulene Sulfinyl Radical OCNSO

Neutral five‐atomic cumulenes formally consisting of two pseudohalogens (e.g., NCO, NNN, NSO) by sharing the central nitrogen atom are exotic species that have been barely studied. Through flash vacuum pyrolysis of CF₃S(O)NCO at ca. 1200 K, sulfinyl isocyanate, bearing resonance structures of O=C−N=S=O and O=C=N−S=O, has been generated in the gas phase and subsequently characterized in cryogenic matrices (Ar and N₂). Its reversible conformational (syn and anti) interconversion and photodecomposition were observed.     

Theoretical Study on the Gas‐Phase SN2 Reaction of Microhydrated Fluoride with Methyl Fluoride

The rate constants for the gas‐phase S_N2 reaction of F^?(H₂O) with CH₃F have been calculated using the dual‐level variational transition state theory including multidimensional tunneling from 50 to 500 K. Tunneling was found to dominate the reaction below 200 K. The deuterium, ¹³C, and ¹⁴C kinetic isotope effects (KIEs) and solvent (D₂O) isotope effects (SKIEs) were also calculated in the same temperature range. The results indicated that the deuterium and heavy water substitutions resulted in inverse KIEs (0.6～0.8 ) while the ¹³C and ¹⁴C substitutions resulted in normal KIEs (1.0～1.2) at room temperature. The calculated carbon KIEs increased significantly below 80 K due to the differences in the magnitude of the tunneling effects for different isotopic substitutions.     

The reaction of photochemically generated CF3O radicals with CO

CF₃O₂CF₃ was photolyzed at 254 nm in the presence of CO in 760 torr N₂ or air at 296 K in a static reactor. In N₂, the products CF₃OC(O)C(O)OCF₃ and CF₃OC(O)O₂C(O)OCF₃ were detected by FTIR spectroscopy. In air, the only observed products were CF₂O and CO₂ and a chain process, initiated by CF₃O, was invoked for the conversion of CO to CO₂. From both product studies, a mechanism for the CF₃O initiated oxidation of CO was derived, involving the addition reaction CF₃O₂ + CO → CF₃OC(O). The rate constant for the reaction CF₃O + CO at 296 K at a total pressure of 760 torr air was determined to be k(CF₃O + CO) = (5.0 ± 0.9) × 10⁻¹⁴ cm³ molecule⁻¹ s⁻¹. © 1997 John Wiley & Sons, Inc.     

Difluorophosphoryl Nitrene F2P(O)N: Matrix Isolation and Unexpected Rearrangement to F2PNO

Triplet difluorophosphoryl nitrene F₂P(O)N (X³A′′) was generated on ArF excimer laser irradiation (λ=193 nm) of F₂P(O)N₃ in solid argon matrix at 16 K, and characterized by its matrix IR, UV/Vis, and EPR spectra, in combination with DFT and CBS‐QB3 calculations. On visible light irradiation (λ>420 nm) at 16 K F₂P(O)N reacts with molecular nitrogen and some of the azide is regenerated. UV irradiation (λ=255 nm) of F₂P(O)N (X³A′′) induced a Curtius‐type rearrangement, but instead of a 1,3‐fluorine shift, nitrogen migration to give F₂PON is proposed to be the first step of the photoisomerization of F₂P(O)N into F₂PNO (difluoronitrosophosphine). Formation of novel F₂PNO was confirmed with ¹⁵N‐ and ¹⁸O‐enriched isotopomers by IR spectroscopy and DFT calculations. Theoretical calculations predict a rather long P? N bond of 1.922 Å [B3LYP/6‐311+G(3df)] and low bond‐dissociation energy of 76.3 kJ mol^?1 (CBS‐QB3) for F₂PNO.     

2,4‐Diamino‐6‐methyl‐1,3,5‐triazin‐1‐ium trifluoroacetate

Crystals of the title compound, C₄H₈N₅⁺·C₂F₃O₂⁻, are built up of singly protonated 2,4‐diamino‐6‐methyl‐1,3,5‐triazin‐1‐ium cations and trifluoroacetate anions. The CF₃ group of the anion is disordered. The oppositely charged ions interact via almost linear N—H...O hydrogen bonds, forming a CF₃COO⁻...C₄H₈N₅⁺ unit. Two units related by an inversion centre interact through a pair of N—H...N hydrogen bonds, forming planar (CF₃COO⁻...C₄H₈N₅⁺...C₄H₈N₅⁺·CF₃COO⁻) aggregates that are linked by a pair of N—H...O hydrogen bonds into chains running along the c axis.     

Kinetics and mechanism of the thermal gas‐phase oxidation of perfluorobutene‐2 in presence of trifluoromethyl hypofluorite

The oxidation of perfluorobutene‐2 (C₄F₈) initiated by trifluoromethyl hypofluorite (CF₃OF) in presence of O₂ has been studied at 323.1, 332.6, 342.5, and 352.0 K, using a conventional static system. The initial pressure of CF₃OF was varied between 4.8 and 23.6 Torr, that of C₄F₈ between 48.7 and 302.4 Torr, and that of O₂ between 51.5 and 270.4 Torr. Several runs were made in presence of 325.5–451.2 Torr of N₂. The main products were COF₂, CF₃C(O)F, and CF₃OC(O)F. Small amounts of compound containing ? CF(CF₃)? O? C(O)CF₃ group were also formed, as detected by ¹³C NMR spectroscopy. The oxidation is a homogeneous short‐chain reaction, attaining, at the pressure of O₂ used, the pseudo‐zero‐order condition with respect to O₂ as reactant. The reaction is independent of the total pressure. Its basic steps are as follows: the thermal generation of CF₃O^? radicals by the abstraction of fluorine atom of CF₃OF by C₄F₈, the addition of CF₃O^? to the alkene, the formation of perfluoroalkoxy radicals RO^? in presence of O₂, and the decomposition of these radicals via the C? C bond scission, giving products containing ? C(O)F end group and reforming RO^? and CF₃O^? radicals. The mechanism consistent with experimental results is postulated. © 2003 Wiley Periodicals, Inc. Int J Chem Kinet 35: 532–541, 2003     

Solid‐State Form Screen of Cardiosulfa and Its Analogues

Cardiosulfa is a biologically active sulfonamide molecule that was recently shown to induce abnormal heart development in zebrafish embryos through activation of the aryl hydrocarbon receptor (AhR). The present report is a systematic study of solid‐state forms of cardiosulfa and its biologically active analogues that belong to the N‐(9‐ethyl‐9H‐carbazol‐3‐yl)benzene sulfonamide skeleton. Cardiosulfa (molecule 1 ; R¹=NO₂, R²=H, R³=CF₃), molecule 2 (H, H, CF₃), molecule 3 (CF₃, H, H), molecule 4 (NO₂, H, H), molecule 5 (H, CF₃, H), and molecule 6 (H, H, H) were synthesized and subjected to a polymorph search and solid‐state form characterization by X‐ray diffraction, differential scanning calorimetry (DSC), variable‐temperature powder X‐ray diffraction (VT‐PXRD), FTIR, and solid‐state (ss) NMR spectroscopy. Molecule 1 was obtained in a single‐crystalline modification that is sustained by N? H???π and C? H???O interactions but devoid of strong intermolecular N? H???O hydrogen bonds. Molecule 2 displayed a N? H???O catemer C(4) chain in form I, whereas a second polymorph was characterized by PXRD. The dimorphs of molecule 3 contain N? H???π and C? H???O interactions but no N? H???O bonds. Molecule 4 is trimorphic with N? H???O catemer in form I, and N? H???π and C? H???O interactions in form II, and a third polymorph was characterized by PXRD. Both polymorphs of molecule 5 contain the N? H???O catemer C(4) chain, whereas the sulfonamide N? H???O dimer synthon R₂²(8) was observed in polymorphs of 6 . Differences in the strong and weak hydrogen‐bond motifs were correlated with the substituent groups, and the solubility and dissolution rates were correlated with the conformation in the crystal structure of 1 , 2 , 3 , 4 , 5 , 6 . Higher solubility compounds, such as 2 (10.5 mg mL^?1) and 5 (4.4 mg mL^?1), adopt a twisted confirmation, whereas less‐soluble 1 (0.9 mg mL^?1) is nearly planar. This study provides practical guides for functional‐group modification of drug lead compounds for solubility optimization.     

Photolysis of Carbonyl Diisocyanate: Generation of Isocyanatocarbonyl Nitrene and Diazomethanone

The stepwise decomposition of carbonyl diisocyanate, OC(NCO)₂, has been studied by using IR spectroscopy in solid argon matrices at 16 K. Upon irradiation with an ArF laser (λ=193 nm), carbonyl diisocyanate split off CO and furnished a new carbonyl nitrene, OCNC(O)N, in its triplet ground state. Two conformers of the nitrene, syn and anti, that were derived from the two conformers of OC(NCO)₂ (62 % syn–syn and 38 % syn–anti) were identified and characterized by combining IR spectroscopy and quantum chemical calculations. Subsequent irradiation with visible light (λ>395 nm) caused the Curtius rearrangement of the nitrene into OCNNCO. In addition to the expected decomposition products, N₂ and CO, further photolysis of OCNNCO with the ArF laser yielded NOCN, through a diazomethanone (NNCO) intermediate. To further validate our proposed reaction mechanism, ArF‐laser photolysis of the closely related NNNNCO and cyclo‐N₂CO in solid argon matrices were also studied. The observations of NOCN and in situ CO‐trapped product OCNNCO provided indirect evidence to support the initial generation of NNCO as a common intermediate during the laser photolysis of OCNNCO, NNNNCO, and cyclo‐N₂CO.     

Synthesis and x‐ray crystal structures of hypervalent hexacoordinate antimony compounds without halogen ligands

Hypervalent hexacoordinate antimony‐ate complex { 2‐Et₄N : Rf₃Sb⁻Et₄N⁺ (Rf: o‐C₆H₄C(CF₃)₂O‐)} was synthesized by the reaction of Rf₂SbCl with lithium 1,1,1,3,3,3‐hexafluoro‐2‐(2‐lithiophenyl)‐2‐propoxide followed by countercation exchange. Reaction of 2‐Et₄N with triethyloxonium tetrafluoroborate gave the O‐ethylated adduct ( 3 ). X‐ray crystallographic analysis of 2‐Et₄N and 3 showed distorted octahedral structures of these compounds. © 2001 John Wiley & Sons, Inc. Heteroatom Chem 12:33–37, 2001     

Mono‐ and dinuclear CuII complexes of the benzyldipicolylamine (BDPA) ligand: crystal structure,synthesis and characterization

The crystal structures of mono‐ and dinuclear Cu^II trifluoromethanesulfonate (triflate) complexes with benzyldipicolylamine (BDPA) are described. From equimolar amounts of Cu(triflate)₂ and BDPA, a water‐bound Cu^II mononuclear complex, aqua(benzyldipicolylamine‐κ³N ,N′ ,N ′′)bis(trifluoromethanesulfonato‐κO )copper(II) tetrahydrofuran monosolvate, [Cu(CF₃SO₃)₂(C₁₉H₁₉N₃)(H₂O)]·C₄H₈O, (I), and a triflate‐bridged Cu^II dinuclear complex, bis(μ‐trifluoromethanesulfonato‐κ²O :O ′)bis[(benzyldipicolylamine‐κ³N ,N′ ,N ′′)(trifluoromethanesulfonato‐κO )copper(II)], [Cu₂(CF₃SO₃)₄(C₁₉H₁₉N₃)₂], were synthesized. The presence of residual moisture in the reaction medium afforded water‐bound complex (I), whereas dinuclear complex (II) was synthesized from an anhydrous reaction medium. Single‐crystal X‐ray structure analysis reveals that the Cu^II centres adopt slightly distorted octahedral geometries in both complexes. The metal‐bound water molecule in (I) is involved in intermolecular O—H…O hydrogen bonds with triflate ligands and tetrahydrofuran solvent molecules. In (II), weak intermolecular C—H…F(triflate) and C—H…O(triflate) hydrogen bonds stabilize the crystal lattice. Complexes (I) and (II) were also characterized fully using FT–IR and UV–Vis spectroscopy, cyclic voltammetry and elemental analysis.     

Chair‐ and Boat‐Configurations of Silver(I) Complexes of Ditopic Ligand Involving Benzimidazolyl Substituents

The ditopic ligand 1, 2‐bis(benzimidazol‐1‐ylmethyl)benzene (L¹) as well as its silver(I) complexes [Ag₂L¹₂(CF₃CO₂)₂] ( 1 ) and [Ag₂L¹₂](CF₃SO₃)₂ · (L¹) · 2H₂O · 0.5C₂H₅OH ( 2 ) were prepared and structures characterized by X‐ray crystallography. The Ag^I atoms in 1 are trigonally coordinated by two N_BIm atoms from the arms of L¹ and by one O atom of the anion CF₃CO₂^—, while those in 2 are only linearly ligated by N_BIm. Different silver salts of CF₃CO₂^— and CF₃SO₃^— lead to different configurations of the dimeric unit [Ag₂L¹₂]²⁺: chair‐form in ( 1 ) but boat‐form in ( 2 ). The discrete molecules in both 1 and 2 are assembled into network structures through face‐to‐face π · · · π stacking and edge‐to‐face C—H · · · π interactions in the crystalline state, as well as N—H · · · O and C—H · · · O hydrogen bonds. Solution ¹H NMR studies showed the formation of one sole species in solution or a rapid equilibrium was established on the NMR time scale at room temperature.     

Umsetzungen von Thiazylhalogeniden XSN (X = F,Cl) mit perfluorierten Iminen Rf2NH (Rf = F,CF3, CF3S, (CF3)2C, (CF3)2 S): Versuche zur Darstellung von Aminothiazylen (N?SN)

Reactions of Thiazyl Halides XSN (X = F, Cl) with Perfluorinated Imines R_f2 NH (R_f = F, CF₃, CF₃S, (CF₃)₂C?, (CF₃)₂S?): Attempted Preparations of Aminothiazyls (?N? S?N) Thiazyl halides or their precursors Cl₃S₃N₃ and FC(O)N?SF₂ react with perfluoro imines to provide the corresponding aminothiazyls as unstable and reactive intermediates. While with HNF₂ or KF · HNF₂ the final products N₂F₄ and S₄N₄ are formed, [(CF₃)₂N]₂Hg reacts with Cl₃S₃N₃ to give CF₃N?CF₂, FSN, and HgCl₂. The expected product CF₃SN?S?NSCF₃ ( 4 ) is obtained from (CF₃S)₂NH or Hg[N(SCF₃)₂]₂ and FSN probably via (CF₃S)₂ NSN. Surprisingly, (CF₃)₂C?NLi forms with ClSN, Cl₃S₃N₃ or [S₃N₂Cl]Cl in the presence of NH₄Cl 4,5-Dihydro-3,3,5,5-tetrakistrifluoromethyl-3H-1λ⁴,2,4,6-thiatriazine ( 6 ) and (CF₃)₂C?NS_xN?C(CF₃)₂ (X = 1, 2) ( 7a, b ) as byproducts. A CsF catalyzed reaction at 70 to 80°C between (CF₃)₂C?NLi and FSN provides low yields of (CF₃)₂C?N? S? N?S?NCF(CF₃)₂ ( 8 ) together with 7a, b. The latter are the only products without CsF. When (CF₃)₂S?NH is treated with FSN, the compounds CF₃SCF₃, S₄N₄, and N₂ are identified. It is shown by ¹⁹F and ¹⁴N-n.m.r. spectroscopy that (CF₃)S?NSN is an unstable intermediate.     

C,N-chelated organotin(IV) trifluoroacetates. Instability of the mono- and diorganotin(IV) derivatives.

The C,N-chelated tri-, di- and monoorganotin(IV) halides react with equimolar amounts of CF₃COOAg to give corresponding C,N-chelated organotin(IV) trifluoroacetates. The set of prepared tri-, di- and monoorganotin(IV) trifluoroacetates bearing the L^CN ligand (where L^CN is 2-(N,N-dimethylaminomethyl)phenyl-) was structurally characterized by X-ray diffraction analyses, multinuclear NMR and IR spectroscopy. In the case of triorganotin(IV) trifluoroacetates and (L^CN)₂Sn(OC(O)CF₃)₂, no tendency to form hydrolytic products, or instability towards the moisture was observed. L^CNRSn(OC(O)CF₃)₂ (where R is n-Bu or Ph) and L^CNSn(OC(O)CF₃)₃ forms upon crystallization from THF in the air mainly dinuclear complexes in which the two tin atoms are interconnected either by hydroxo-bridges or by an oxo-bridge and/or by a bridging trifluoroacetate(s). In the case of hydrolysis of L^CN(n-Bu)Sn(OC(O)CF₃)₂, a zwitterionic stannate of formula L^CN(n-Bu)Sn(OC(O)CF₃)₂·CF₃COOH was isolated from the mother liquor, too. Products of hydrolysis of L^CN(n-Bu)Sn(OC(O)CF₃)₂ and L^CNSn(OC(O)CF₃)₃, and some other oxygen bridged organotin(IV) compounds containing the same ligand, were tested as possible catalysts of some transesterification reactions as well as in direct dimethyl carbonate (DMC) synthesis from CO₂ and methanol.     

[2+4] and [2+2] Cycloaddition Reactions of N‐Sulfinyl Carboxylic Acid Amides with (CF3)2BNMe2. Crystal Structure of cyclo‐(CF3)2B‐NMe2‐S(=O)‐N=C(p‐CH3C6H4)‐O

N‐sulfinylacylamides R‐C(=O)‐N=S=O react with (CF₃)₂BNMe₂ ( 1 ) to form, by [2+4] cycloaddition, six‐membered rings cyclo‐(CF₃)₂B‐NMe₂‐S(=O)‐N=C(R)‐O for R = Me ( 2 ), t‐Bu ( 3 ), C₆H₅ ( 4 ), and p‐CH₃C₆H₄ ( 5 ) while N‐sulfinylcarbamic acid esters R‐O‐C(=O)‐N=S=O react with 1 to yield mixtures of six‐membered (cyclo‐(CF₃)₂B‐NMe₂‐S(=O)‐N=C(OR)‐O) and four‐membered rings (cyclo‐(CF₃)₂B‐NMe₂‐S(=O)‐N(C=O)OR) for R = Me ( 6 and 9 ), Et ( 7 and 10 ), and C₆H₅ ( 8 and 11 ). The structure of 5 has been determined by X‐ray diffraction.     

CF3CH(ONO)CF3: Synthesis,IR spectrum,and use as OH radical source for kinetic and mechanistic studies

The synthesis, IR spectrum, and first‐principles characterization of CF₃CH(ONO)CF₃ as well as its use as an OH radical source in kinetic and mechanistic studies are reported. CF₃CH(ONO)CF₃ exists in two conformers corresponding to rotation about the RCO? NO bond. The more prevalent trans conformer accounts for the prominent IR absorption features at frequencies (cm^?1) of 1766 (N?O stretch), 1302, 1210, and 1119 (C? F stretches), and 761 (O? N? O bend); the cis conformer contributes a number of distinct weaker features. CF₃CH(ONO)CF₃ was readily photolyzed using fluorescent blacklamps to generate CF₃C(O)CF₃ and, by implication, OH radicals in 100% yield. CF₃CH(ONO)CF₃ photolysis is a convenient source of OH radicals in the studies of the yields of CO, CO₂, HCHO, and HC(O)OH products which can be difficult to measure using more conventional OH radical sources (e.g., CH₃ONO photolysis). CF₃CH(ONO)CF₃ photolysis was used to measure k(OH + C₂H₄)/k(OH + C₃H₆) = 0.29 ± 0.01 and to establish upper limits of 16 and 6% for the molar yields of CO and HC(O)OH from the reaction of OH radicals with benzene in 700 Torr of air at 296 K. © 2003 Wiley Periodicals, Inc. Int J Chem Kinet 35: 159–165, 2003     

Bis­[bis­(pyrimidin‐2‐yl‐κN)­amine](dicyan­amido‐κN1)(tri­fluoro­methanesulfonato‐κO)copper(II) ethanol hemisolvate forms a hydrogen‐bonded chain

In the crystal structure of [Cu(CF₃SO₃)(C₂N₃)(C₈H₇N₅)₂]·0.5C₂H₆O, the Cu^II atom adopts a distorted octahedral geometry, with the basal plane formed by two N atoms of one dipyrimidinyl­amine ligand, one N atom of the second pyrimidine ligand and a nitrile N atom of the dicyan­amide anion [Cu—N = 1.972 (2)–2.021 (2) Å]. The apical positions are occupied by an N atom of the second ligand [Cu—N = 2.208 (2) Å], and an O atom of the tri­fluoro­methane­sulfonate anion [Cu—O = 2.747 (2) Å] at a semi‐coordination distance. Pairs of inversion‐related N—H⋯N hydrogen bonds of the so‐called Watson–Crick type, augmented by two C—H⋯N contacts, link adjacent complexes into an infinite one‐dimensional chain running in the [101] direction.     

[Pd(Fmes)2(tmeda)]: A Case of Intermittent C?H⋅⋅⋅F?C Hydrogen‐Bond Interaction in Solution

The X‐ray structure of the title compound [Pd(Fmes)₂(tmeda)] (Fmes=2,4,6‐tris(trifluoromethyl)phenyl; tmeda=N,N,N′,N′‐tetramethylethylenediamine) shows the existence of uncommon C? H???F? C hydrogen‐bond interactions between methyl groups of the TMEDA ligand and ortho‐CF₃ groups of the Fmes ligand. The ¹⁹F NMR spectra in CD₂Cl₂ at very low temperature (157 K) detect restricted rotation for the two ortho‐CF₃ groups involved in hydrogen bonding, which might suggest that the hydrogen bond is responsible for this hindrance to rotation. However, a theoretical study of the hydrogen‐bond energy shows that it is too weak (about 7 kJ mol^?1) to account for the rotational barrier observed (ΔH^≠=26.8 kJ mol^?1), and it is the steric hindrance associated with the puckering of the TMEDA ligand that should be held responsible for most of the rotational barrier. At higher temperatures the rotation becomes fast, which requires that the hydrogen bond is continuously being split up and restored and exists only intermittently, following the pulse of the conformational changes of TMEDA.     

Oxydifluoromethylation of Alkenes by Photoredox Catalysis: Simple Synthesis of CF2H‐Containing Alcohols

We have developed a novel and simple protocol for the direct incorporation of a difluoromethyl (CF₂H) group into alkenes by visible‐light‐driven photoredox catalysis. The use of fac‐[Ir(ppy)₃] (ppy=2‐pyridylphenyl) photocatalyst and shelf‐stable Hu's reagent, N‐tosyl‐S‐difluoromethyl‐S‐phenylsulfoximine, as a CF₂H source is the key to success. The well‐designed photoredox system achieves synthesis of not only β‐CF₂H‐substituted alcohols but also ethers and an ester from alkenes through solvolytic processes. The present method allows a single‐step and regioselective formation of C(sp³)–CF₂H and C(sp³)?O bonds from C=C moiety in alkenes, such as hydroxydifluoromethylation, regardless of terminal or internal alkenes. Moreover, this methodology tolerates a variety of functional groups.