Alkyl 2-naphthoate

Wu et al. investigated the photodimerization of alkyl 2-naphthoates 76a,b (Scheme 1.14) in the presence of CB[8]. The solubility of 76a,b in water was enhanced upon addition of CB[8]. As a result of 1 2 host-guest complexation between CB[8] and 76, photodimerization reaction rate was greatly accelerated in aqueous solution to give cubane-Uke photodimers 77a,b. 

Lei L, Luo L, Wu X-L, Liao G-H, Wu L-Z, Tung C-H. Cucurbit[8]uril-mediated photodimerization of alkyl 2-naphthoate in aqueous solution. Tetrahedron Lett 2008 49 1502-5. 

Coleman et al. have performed a preliminary structure/activity study for a series of analogues of 77 [149]. They found that removal of the naphthoate moiety (88 Scheme 11.11) dramatically reduced the yield of DNA alkylation, while replacement of the NH2 group with O-benzyl (89 and 90) abolished DNA alkylation completely. Compound 91 alkylated DNA with reduced efficiency, so this effect is not simply due to a requirement for a hydrogen bond donor at this position. Perhaps the amide is required at this position to increase the ability of the C=0 to act as a hydrogen bond acceptor. Importantly, they found a strong correlation between the extent of in vitro DNA alkylation and cell culture cytotoxicity. 

Very recently, the Shipman group have made a further step towards a comprehensive structure/activity profile for noncovalent interactions between azinomycin B and DNA [152]. They synthesized simplified azinomycin analogues 69 and 96-98 (Scheme 11.13), retaining both the epoxide and aziridine alkylating functionalities, with systematically altered substitution on the naphthoate fragment, and analyzed their DNA crosslinking by gel electrophoresis. They found that cross-... 

The current procedure starts with the ester, ethyl 1-naphthoate, and converts it into homologated product in 81% yield without isolation of any intermediates. Safe, commercially available materials are employed. Based on a recently published variation43 of our original homologation methods,4 1 It represents a general procedure applicable to esters 1 bearing aryl, alkenyl, alkynyl and primary, secondary or tertiary alkyl attachments R. Yields range from 67-90% (on a 25-mmol scale) and like the Arndt-Eistert sequence this procedure affords retention of stereochemistry for the... 

A soln. of 5.0 g. ethyl 8/, 8a/ -dimethyl-l-oxo-l,2,3,4,6,7,8,8a-octahydro-2-naph-thoate in hexamethylphosphoramide added at 5° under Ng to a stirred mixture of a 60%-dispersion ofNaHin mineral oil and hexamethylphosphoramide, stirring continued 1 hr. at room temp., cooled to 5°, 1.93 g. chloromethyl methyl ether added, and stirred 2 hrs. at room temp. 5.7 g. crude methoxymethyl enol ether dissolved in ether, added rapidly with Dry Ice-cooling under argon to a stirred dark blue soln. of Li in anhydrous NH3, and stirring continued 12 min. at -33°, the b. p. of liq. NHg 2.85 g. ethyl 8/, 8ai -dimethyl-l,2,3,4,6,7,8,8a-octahydro-2j -naphthoate. Overall Y 60%. - 0-Alkylation of the startg. -keto esters occurs under the above conditions to the complete exclusion of the C-alkylated isomer. The subsequent reduction gives the less stable axial isomer. R. M. Coates and J. E. Shaw, J. Org. Chem. 35, 2597 (1970) f. e. s. ibid. 35, 2601 carboxylic acids, also from a,/ -ethylenecarboxylic acids, cf. ibid. 36, 1151 (1971). 

Selective photodimerization of (99) in a cucurbit[8]uril (CB[8]) as a host in aqueous solution occurred to give a n-head-to-head cyclodimer (261), although (99) in cyclohexane afforded u n-head-to-tail and s jw-head-to-tail dimers (262) and (263). Wu and Tung found the diastereoselective photodimerization of alkyl 3-alkoxy-2-naphthoates (264) giving cage products (266) vis [4 + 4] cycloadducts (265). 

Methyl 8-benzhydryl-l-naphthoate added to excess methyllithium prepared from methyl iodide and lithium in ether, and the product isolated after 5 hrs. refluxing methyl 8-benzhydryl-l-naphthyl ketone. Y 92%.—A second mole of methyllithium enolizes the ketone with formation of methane, a general type of reaction of hindered alkyl ketones. Phenyllithium yields a tert. carbinol since enolization of the intermediate is not possible. R. L. Letsinger and P. T. Lans-bury, Am. Soc. 81, 935 (1959). 

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