Allene-ynes

Pauson-Khand-type reactions of enynes are mediated by other metal complexes, such as Fe(CO)5 [100], [W(CO)5THF] and Mo(CO)6 [101]. Cyclization of the allene-yne system 227 to the a-methylenecyclopentenone 228 is promoted by Mo(CO)6. The products depend on the substituents of the allene, and the cyclization of 229 afforded 230 as the main product [102]. 

Cycloaddition. A synthesis of bicyclic dienones by the Pauson-Khand reaction of an allene/yne is based on catalysis by Co2Rh2. Two molecules of an allene combine with CO to form 4-alkylidene-2-cyclopentenones. ... 

A new Ni-catalysed carbocyanative cyclization of allene-ynes and bis-allenes has been reported. The reaction starts with the regioselective hydronickelation of the allene moiety, which is followed by cyclization via carbometalation. ... 

Scheme 8.26 Proposed mechanism for Rh(I)-catalyzed cyclization of allenal-yne.

In toluene, an intramolecular [2+2+2] cyclization of allene-yne-enes was performed to produce tricyclic compounds [106] [Eq. (45)]. 

A ruthenium(II)-catalysed intramolecular [2 + 2 -i- 2] cyclization of allene-yne-enes has been reported to proceed via a ruthenacyclopentene intermediate formed from the allene-yne or ene-yne moiety to give tricyclic compounds stereospecifically (Scheme 158).2°4... 

Sote 1. In the final stage of the distillation the remaining liquid is subjected to a relatively higli temperature. This causes dimerization of the greater part of the yne-allene RCeC-CH=C=CH2, which is formed as a by product. 

Treating diene-yne derivatives 50 with ferrate 40 does not lead to the expected ene-allenes, instead the [4 + 2]-cycloaddition products 51 are obtained in moderate yields (eq. 1 in Scheme 11). As metal-catalyzed Diels-Alder-reactions of unactivated aUcynes and dienophiles are assumed to proceed via metaUacyclic intermediates, this supports the mechanism for the Alder-ene-reaction discussed before. 

The [(T -C3H5)PdCl]2/dppf/AcOH catalytic system has been used for the bis(hy-droamination) of 3-alken-l-ynes to alkenic 1,4-diamines (Eq. 4.94), a reaction which seems to be mechanistically related to the hydroamination of allenes since an a-al-lenic amine CH2=C=CH(R )CH2NR2 is believed to be an intermediate [318]. 

This Pd(0)/formic acid system was effective for the cyclization of substituted 5-allene-l-ynes to give diene 140 (Eq. 25) through initial insertion into the internal 7r-bond of the allene followed by insertion into the alkyne [79]. All of the examples provided were geminally substituted within the backbone to facilitate cyclization. Intramolecular allene-alkyne reductive couplings to generate six-membered rings were not achieved. 

Finally, thermally induced isomerizations which generate carbon-centered biradical organic molecules have been shown to serve as alternative for conventional chemical and photochemical methods [71]. A straightforward procedure to accomplish such biradicals was described by Myers using a thermal conversion of yne-allenes [72]. According to this scheme, Wang and coworkers [73] heated 3-178 in 1,4-cyclohexadiene to 75 °C and obtained 3-181 in 22% yield via the biradicals 3-179 and 3-180 (Scheme 3.48). 

It should be mentioned that the same group has also developed a related method in which benzoene-yne-allenes were cydized via biradicals in a domino-like manner [131],... 

Burger2 has shown that alkynes undergo both Lewis acid-catalyzed and thermal carbonyl-yne reactions with 3,3,3-trifluoropyruvates to give allenes. Reaction of 1 (Equation (2)) occurs to give a 1 1 mixture of diastereomeric allenyl carbinols 2. Alternatively, reaction of hexyne 1 and methyl trifluoropyruvate with MgBr2-OEt2 at low temperature afforded 2 as an 8 1 mixture of diastereomers. The thermal reaction does not suffer from allylic alcohol byproducts arising from reaction of the substrate with the Lewis acid.3... 

Product stabilization is much more pronounced when the enediyne or ene-yne-allene starting materials are not already part of an aromatic system, since forming an aromatic system constitutes a much higher degree of stabilization than expanding an aromatic system (Fig. 24). Conjugation of the radical center provides additional stabilization to the 71-radical formed by the Myers-Saito and Schmittel cyclizations. 

The intramolecular cyclization of l,2-dien-7-ynes and l,2-dien-6-ynes regiospecifically affords the corresponding titanacycles, which react with protons, carbon monoxide, aldehydes, or imines to give single products, as shown in Eqs. 9.56 and 9.57 [102], As the formation of titanacycles and their subsequent reaction with externally added reagents such as carbon monoxide (Eq. 9.56) or an aldehyde (or imine) (Eq. 9.57) proceeds with excellent chirality transfer, this represents a new method for synthesizing optically active cyclopentane derivatives from optically active allenes [102]. 

The hydrosilylation of l,4-bis(trimethylsilyl)but-3-en-l-yne (141) was beautifully controlled and four different isomeric products could be prepared independently with 93-96% selectivity by a proper choice of geometric isomers of 141 and transition metal catalysts [113]. One of the four products from the reaction of 141 with 132p was allene 142, which was obtained as a mixture (142 143 = 96 4) in 93% yield (Scheme 3.73). 

The ruthenium-catalyzed hydrosilylation of l-(trimethylsilyl)but-l-en-3-yne (144) also afforded an allenic species 145 as a main product [114]. A product mixture of five species was formed and the allene 145 was obtained with up to 92% selectivity (Scheme 3.74). 

In 2001, a palladium-catalyzed asymmetric hydrosilylation of 4-substituted-but-l-en-3-ynes (146) was reported by Hayashi and co-workers [115]. It was found that a monodentate bulky chiral phosphine, (S)-(R)-bisPPFOMe, was effective for the asymmetric synthesis of the axially chiral allenes 147 and up to 90% ee was achieved (Scheme 3.75). The bulky substituent at the 4-position in 146 is essential for the selective formation of the allene 147 the reaction of nC6H13C=CCH=CH2 gave a complex mixture of hydrosilylation products which consisted of <20% of the allenylsilane. 

A single example of allene formation was briefly described for a reaction of 2-methylbut-l-en-3-yne (148) with catecholborane (149) [116]. The allenylborane 150 was not isolated but converted into the homopropargyl alcohol 151 in 57% yield by quenching with benzaldehyde (Scheme 3.76). 

To prepare the parent bisallene 118, 116 is first converted into its Grignard reagent (known from spectroscopic studies to possess the allenic structure), from which, presumably, by the addition of cuprous chloride the organocopper intermediate 117 is generated. Addition of further 116 subsequently provides a mixture of 118 and propargylallene (l,2-hexadien-5-yne) (29) (see below) in a 2 3 isomer ratio [44],... 

The reaction sequence to the latter hydrocarbons is the most flexible one and starts from the allenic alcohols 212, which are first converted to the l,3-hexadien-5-ynes 213 by an elimination reaction the allene group is then generated by a pro-pargylic rearrangement initiated by the addition of a Grignard reagent. 

The nucleophilic attack on an acceptor-substituted allene can also take place at the acceptor itself, especially in the case of carbonyl groups of aldehydes, ketones or esters. Allenic esters are reduced to the corresponding primary alcohols by means of diisobutylaluminum hydride [18] and the synthesis of a vinylallene (allenene) by Peterson olefination of an allenyl ketone has also been reported [172]. The nucleophilic attack of allenylboranes 189 on butadienals 188 was investigated intensively by Wang and co-workers (Scheme 7.31) [184, 203, 248, 249]. The stereochemistry of the obtained secondary alcohol 190 depends on the substitution pattern. Fortunately, the synthesis of the desired Z-configured hepta-l,2,4-trien-6-ynes 191 is possible both by syn-elimination with the help of potassium hydride and by anti-elimination induced by sulfuric acid. Analogous allylboranes instead of the allenes 189 can be reacted also with the aldehydes 188 [250]. 

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