Enediynes, synthesis

Koenig, B., Pitsch, W., Klein, M., Vasold, R., Prall, M., Schreiner, P. R. Carbonyl- and Carboxyl-Substituted Enediynes Synthesis, Computations, and Thermal Reactivity. J. Org. Chem. 2001, 66,1742-1746. 

Scheme 31. cii-Enediyne synthesis via a bis(alkynylcarbene) intermediate. (Tol = Tolyl.)... 

Unsaturated Azamacrocyclic Enediynes Synthesis, Structural Analysis and Thermal Behavior... 

O Connor, J.M., Baldridge, K.K., Rodgers, B.L., et al. (2010) A photochemical metallocene route to anionic enediynes synthesis, solid-state structures, and ab initio computations on cyclopentadienidoenediynes. Journal of the American Chemical Society, 132(32), 11030-11032. 

Gonzalez, 1., Roglans, A., Benet-Buchholz, J. and Rourac, P. (2006) New unsaturated azamacrocyclic enediynes synthesis, structural analysis and thermal behavior. Synlett, (18), 3041-3044. 

Design and synthesis of analogs of dynemycin, antitumor antibiotic with an-thraquinone, 10-member enediyne, tetrahydropyridine, and oxirane fragments 99EJ01. 

Enediynes with ethylene carbonate fragment in the synthesis of dienediyne models of the biradical-forming and DNA-cleaving natural neocarzinostatin chromophore 99SL657. 

The anticancer activity of complex natural products having a cyclodecenediyne system [for a review see <96MI93>] has prompted the synthesis of 54 (X = CH2 and OCH2) <96CC749> and 55 (R = a-OH and p-OH) <95AG(E)2393> on the basis that such compounds are expected to develop anticancer activity as the P-lactam ring opens. This is because cycloaromatization can only occur in the monocyclic enediyne and the diradical intermediate in the cyclization is thought to be the cytotoxic species. 

The Pd°-catalyzed transformation of enediynes represents a highly efficient and effective approach for the synthesis of polycyclic compounds, with different ring sizes being obtained by a variation of the tether [129]. In this respect, reaction of 6/1-270 led to the tricyclic product 6/1-271 as a single diastereomer. The initial step is a chemoselective hydropalladation of the propargylic ester moiety in 6/1-270 to give an alkenyl-Pd-species, according to the mechanism depicted in Scheme 6.71. A hexatriene is formed as a byproduct. 

A domino Pauson-Khand-Reaction was developed by Keese et al. starting from enediyne 155 leading to the shortest synthesis of a fenestrane 157 (scheme 31).1791... 

Scheme 20.22 Synthesis of 11 H-benzo[fo]fluorenes via prototropic rearrangement of benzannulated enediynes.

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