Copper iodo complexes

Many of the iodo complexes may be prepared from copper(I) iodide by the reaction... 

Shin, M., Umebayashi, Y., Kanzaki, R., andlshiguro, S. I. (2000). Formation of copper(II) thiocyanato and cadmium(II) iodo complexes in micelles of nonionic surfactants with varying polyethylene chain length. J. Colloid Interface Sci. 225(1), 112-118. 

Furan derivatives are prepared by reaction of o-iodophenols. 2-Phenylbenzo-[ >]furan was prepared by the reaction of o-iodophenol (64) with 1-alkyne in one step [40]. It should be noted that similar 2-arylbenzo[i>]furan formation occurred by the use of Pd-free, copper-phosphine complex [41]. Similarly 2-substituted furo[3.2-i ]pyridine 66 was prepared from 2-iodo-3-pyridinol (65) in a one-pot reaction [42]. Naturally occurring ailanthoidol was synthesized by the reaction of 67 and 68 to give the cyclized product 69 [43]. 

Preparation of the double-stranded helical precursor with copper(l) using the 1,3-phenylene linker turned ont to be qnantitative. Reaction of this tetraphenolic donble helix with two eqnivalents of the di-iodo derivative of hexaethyleneglycol, in the presence of caesinm carbonate, afforded a single isolable copper(I) complex the dicopper(l) knot was isolated in 29% yield after chromatography. H-NMR spectroscopy data indicated that the knot contained a compact helical core. This was fully confirmed by its subsequent X-ray strnctnre determination. The spectacularly improved yield can be increased even further by optimizing the covalent-bond-forming reactions, whose conditions can harm the helical precnrsors. 

We have recently reported that the air-stable and hydrosoluble iminophosphorane copper(I) complex 6 is also active in CuAAC of 1-iodoalkynes in aqueous media, under mild and aerobic conditions according to click laws and displaying a broad substrate scope and functional compatibility [29] (see Scheme 15.8). It is important to note the following catalytic features (i) catalyst 6 was the first example of an isolated and crystallographically characterized copper(I) catalyst active for cycloaddition of 1-iodoalkynes with azides, to give 5-iodo-1,2,3-triazoles exclusively, (ii) The presence of a free thio moiety in the substrate does not deactivate the catalyst, a fact generally observed in CuAAC for functionalized substrates... 

Photolytically generated carbene, as mentioned above, undergoes a variety of undiscriminated addition and insertion reactions and is therefore of limited synthetic utility. The discovery (3) of the generation of carbenes by the zinc-copper couple, however, makes carbene addition to double bonds synthetically useful. The iodo-methylzinc iodide complex is believed to function by electrophilic addition to the double bond in a three-center transition state giving essentially cis addition. Use of the... 

Bromothiophene has been coupled with phenylacetylene in a copper-free reaction to give a 96% yield of the product (Equation 33) <20030L4191>. A Pd(ll) complex containing the ferrocene-based phosphinimine-phosphine ligand 83 has proved very efficient for the reaction of 2-iodo- and 2-bromothiophene with phenylacetylene the coupling takes place under copper- and amine-free conditions (Equation 34) <2004TL4337>. 

Preparation. A solution of 2 eq. of vinyllithium (Alfa Inorganics) in THF is added slowly to aTHF.solution of 1 eq. of letrakis[iodo-(tri-ii-bulylphospliine)copper(l)] (2, 400 3, 278) at —78° under Nj with stirring. The complex is blue-black. 

A similar complex has been used in a recent synthesis of (+ )-l S-desoxyprostaglandin E,Thus reaction of (1) with 2 molar cq. of l-lithio-rraras-octene-l in the presence of 1 eq. of tetrak is[iodo-( tri-n-butylphosphine)copper( I)] in ether at 0° gives, after hydrolysis of the tctrahydropyranyl protecting group, (+)-15-desoxyprostaglandin E ethyl ester (2) in 60% yield. 

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