Butadiene lactone synthesis

Braunstein P, Matt D, Nobel D (1988) Carbon-dioxide activation and catalytic lactone synthesis by telomerization of butadiene and C02. J Am Chem Soc 110 3207-3212... 

Although much less prevalent than the use of CO in lactone synthesis, direct incorporation of CO2 for the synthesis of lactones is advantageous due to lower toxicity while maintaining high atom efficiency. Louie and coworkers demonstrated that a formal [2 + 2 + 2] cycloaddition of bis-alkynes with CO2 yields pyrone derivatives under Ni(0) catalysis (Scheme 2.62) [117]. It is proposed that an initial cydometallation of one alkyne and CO2 yields a Ni(II) metallacycle, followed by insertion of the other alkyne and reductive elimination. Pd(0) has also demonstrated catalytic activity in carboxylations of methoxyallene [118] and 1,3-butadiene [119]. 

Palladium (0)-Catalyzed Telomerization of Butadiene with C02 Synthesis of S-Lactone I 113... 

However, excellent simple (exo endo = 95 5) and induced diastereoselectivity (94 6) was obtained by Jurczak [88] by applying the bornane sulfone amide derivative of glyoxylic acid 2-23 in the presence of a catalytic amount of a europium salt. Reaction of 2-23 with 1-methoxy-1,3-butadiene 2-24 gave predominantly 2-25 a which was transformed into the lactone 2-26 aiming towards the synthesis of compactin (Fig. 2-7)[89]. 

A related cyclocondensation using bis-1,1 -dinu thoxy-3-trimcthylsilyloxy-1,3-butadiene provides a synthesis of 3-keto-8-lactones (equation 111). ... 

Some studies directed at the synthesis of the b + c + d rings of gibberellic acid, and in particular the fragment (134), have been reported.The Diels-Alder addition of butadiene to the cyclopentenone (135) afforded (136), which was converted via its iodo-lactone (137) into the tricyclic compound (138). However, the synthesis broke down at the removal of the ring D substituents. l-Hydroxy-7-methylenebicyclo[3,2,l]octane (139) provides a model for the gibbane-steviol c/d ring system. A synthetic route involves the photoaddition of allene to 1-cyclopentene-l-aldehyde to give l-formyl-7-methylenebicyclo-... 

There is an ongoing interest in catalytic C-C bond-forming reactions of CO2 [3] and much work has been invested in palladium-catalyzed synthesis of 5-lactone 2 from butadiene 1 and CO2 [3 e, 3 f, 4]. Table 1 presents the catalyst development for this catalytic coupling reaction, and the optimum conditions as known up to now are summarized in eq. (1). 

Abstract This review deals with the synthesis and the catalytic application of noncyclopentadienyl complexes of the rare-earth elements. The main topics of the review are amido metal complexes with chelating bidentate ligands, which show the most similarities to cyclopentadienyl ligands. Benzamidinates and guanidinates will be reviewed in a separate contribution within this book. Beside the synthesis of the complexes, the broad potential of these compounds in homogeneous catalysis is demonstrated. Most of the reviewed catalytic transformations are either C-C multiple bond transformation such as the hydroamination and hydrosilylation or polymerization reaction of polar and nonpolar monomers. In this area, butadiene and isoprene, ethylene, as well as lactides and lactones were mostly used as monomers. 

SCHEME 6.18 Synthesis of 2-ethylheptanol from the S-lactone obtained in telomerization of C02 and butadiene. 

The optimized reaction conditions cited above enabled the synthesis of the lactone in a technical scale. Using a T 1 autoclave more than 100 g of the lactone could be produced per experiment. The 6-lactone could be isolated by vacuum distillation or water steam distillation in purities higher than 99 %, because under the optimized conditions no interfering by-products of CO2 and butadiene are formed. 

The novel isolated complex is itself a good catalyst for the synthesis of the 6-lactone. Further addition of a phosphine is not necessary that means that this palladium complex is a real one-component-catalyst in the reaction of butadiene and carbon dioxide. 

The dimerization of butadiene is a useful method for the synthesis of various natural products. Pellitorine, which is an insecticidal compound isolated from Amcydkm pyrethrum roots, queen substances, which are well-known honey bee pheromones, ds-dvetone, which is a naturally occurring unique symmetric 17-manbered cyclic ketone, and recifeiolide, which consists of a 12-membered lactone firamwork, can readily be synthesized from butadiene dimers. 

In synthesis of isotetronic acid derivatives, aldol-type reactions of 1,2-dicarbonyl substrates including oxalyl chloride and pyruvates are used as powerful mefhodologies. For instance, Langer et al. reported systematic investigations on such reaction of oxalyl chloride 21 wifh l,3-bis(trimethylsilyloxy)-l,3-butadienes 22 or 24 as masked dianion equivalenfs (Scheme 10) [21]. By using a catalytic amoxmt of MesSiOTf, y-lactone formation smoothly occurred to yield the lactones (E)-23 or (Z)-25, respectively. This methodology is also effective for the synthesis of medium-sized bicyclic y-bufenolides such as 25c [22]. 

This methodology was initially applied to a synthesis of (—)-alloyohimbane (82) (Scheme 3.13) (29). Readily available levoglucosenone (75), a product of cellulose pyrolysis, was the starting material. Diels-Alder reaction of 75 with 1,3-butadiene afforded adduct 76 which underwent Wolff-Kishner elimination and subsequent acylation to provide the bicyclic enol ether 77. Hydrolysis followed by oxidation and saponification afforded hydroxymethyl lactone 78 which was then condensed with tryptamine to yield the amide diol 79. Periodate cleavage of the diol was followed by conversion to chloride 80 which was cyclized to afford lactam 81. Subsequent Bischler-Napieralski cyclization followed by hydrogenation of the olefin moiety afforded the target ( )-alloyohimbane (82). 

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