Cobalt propargyl substitution

The reaction of propargyl alcohols with dicobalt octacarbonyl to give the complex salts 148 (X = BF4 or PF6) and synthetic uses of the latter have been reviewed. The salts react with electron-rich aromatic compounds ArH, such as anisole, phenol or N,N-dimethylaniline, to yield substitution products 149 after oxidative demetallation with an iron(III) or cerium(I V) salt with j5-diketones or j -keto esters the corresponding propargyl-substituted compounds 150 are obtained k Acetone reacts in an analogous fashion to give 151. The action of the cobalt complexes 148 on allylsilanes 152 leads to enynes 153. Indole reacts with the complex 148 (R = H R = R = Me) in the presence of boron trifluoride etherate to give 154, which was converted into 155 by the action of iron(III) nitrate " ... 

An underused property of cobalt-coordinated alkynes is the stabilization of propargyllic cations. The Nicholas reaction is a propargylic substitution reaction facilitated by the ability of the adjacent cobalt complex to stabilize the propargylic cation, 67 to 68. Both carbon and heteroatom nucleophiles have been used to effect this transformation. " This transformation has been been used as a strategy to introduce the alkene component for an intramolecular PKR. Shea has probed the use of an... 

Many examples exist of alkynophylic metals other than cobalt that also promote propargylic substitution reactions rhenium, ruthenium, and gold can all be useful substitutes for cobalt. For example, Campagne synthesized enyne 18 upon treatment of propargyl alcohol 17 with allyltrimethylsilane and a Au(III) catalyst. ... 

Substituted phthalides can be prepared in a [2+2+2] cycloaddition of two molecules of methyl propiolate with propargyl alcohol. This cyclotrimerization, which is catalyzed by a cobalt(ll)-DPPE complex in the presence of catalytic amounts of zinc, affords the reaction products in acceptable to good yields (Equation 150) <2005CC4955>. 

Alkynols complexed to cobalt can be oxidized to alkynals without decomplexation. Propargyl aldehydes are protected from polymerization upon complexation with Co2(CO)6. These aldehydes smoothly undergo Wittig-type reactions. Carbonyl-ene reactions have been demonstrated (Scheme 194). Complexation to cobalt protected the enyne in complex (132) from Michael-type reactions (Scheme 195). Alkenyl-substituted complexes undergo [3 + 2]cycloadditions with nitrile A-oxides (Scheme 196). 

The facile acid-promoted dehydration of cobalt-complexed propargyl alcohols [18], via P-pro-ton loss from the derived cations (Scheme 4-50) offers improved chemo-, regio- and stereoselectivity vis a vis the free propargylic alcohols, with a strong preference for the more substituted ( )-ene-yne complex [151,152]. Such Co-mediated dehydration has afforded routes to enantiomerically pure manicone and normanicone (4,6-dimethyl-4-octen-3-one,... 

A concise synthesis of substituted stUbenes from propargylic phosphonium salts by a cobalt-catalyzed Diels-Alder/Wittig olefination reaction has been described (Figure 1.4) [37]. It was shown that the cobalt(I)Diels-Alder reaction of propargylic phosphonium salts and alkyne-fimctionalized phosphonium salts with 1,3-dienes led to dihydroaromatic phosphonium salt intermediates that were directly used in a one-pot Wittig-type olefination reaction with aldehydes. Subsequent oxidation led to styrene- and stUbene-type products with the formation of three new carbon-carbon bonds. The reaction gives predominantly the Econfigured products. 

The Nicholas reaction enables efficient substitution reactions of propargyl alcohols, ethers, and acetates. Prior to the substitution step, dicobalt octacarbonyl reacts with the alkyne to yield cobalt-alkyne complex 1. The resulting organometallic complex reacts with inter- or intramolecular nucleophiles in the presence of a Lewis or protic acid to furnish desired substitution products 2. The cobalt-complexed alkyne can be oxidatively removed after this step or used to further fiinctionalize the Nicholas reaction products. The stereoselective synthesis of chiral products using the title reaction is also possible. ... 

As part of his research into the synthesis of oxygen-bridged nine- and ten-membered cycloalkanes, Montana introduced a key carbon fragment via the Nicholas reaction. Boron trifluoride promoted reaction between silyl enol ether 28 and cobalt-alkyne complexed propargyl alcohol 29 provides substitution product 30 in excellent yield. ... 

The cobalt-catalyzed [2+2+2] cycloaddition of 4-hydroxy-substituted enediynes [152] that has been implemented in the synthesis of 2-hydroxy substituted decahydrophenanthrenes [153] has shown that the hydroxy group in the propargyl position tolerates the chosen reaction conditions. So, this approach could be an appropriate route to hydrogenated trans-phenanthrenes, which are the ABC cores of ergosterin and lumisterin steroids. This was a reason to consider the diastereoselective synthesis of (3S)-hydroxyandrosta-5,7-diene-17-ones 2.307, the precursors of vitamin D, via a D ABCD approach. 

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