1-Naphthyl moieties

Heating the carbamoylated chloroenamine 20b,d/21b,d in acetonitrile in the presence of N,N-diisopropylethylamine without adding a nucleophile gave pentacyclic lactams 23b,d in 15 and 51% yield, respectively. In this case the Af-(1-naphthyl) moiety acts as an intramolecular nucleophile. ... 

Tarzia et al. [69, 70] have recently reported the FAAH inhibitory activity of a series of alkylcarbamic acid aryl esters. The starting point for their studies was the known serine hydrolase inhibitor carbamyl (51) that had no activity at FAAH. Replacement of the small methyl group of carbamyl (51) with more lipophilic groups and, in particular, bulky lipophilic groups resulted in increased affinity at FAAH (Table 6.6). Exploration of replacements of the naphthyl moiety revealed that replacement with a biphenyl group resulted in improved affinity and in particular, the 3-biphenylyl group proved effective... 

A light-controlled dendritic box was investigated in analogous fourth-generation POPAM dendrimers whose periphery alternately bore azobenzene and naphthyl moieties. Measurements of photoisomerisation at a wavelength of 365 nm in dichloromethane showed that not all azobenzene units in the E form are transformed into the Z form, but that, for example, four units remain in the E form and some 28 units isomerise to the Z form. At pH 7, six eosin molecules per host molecule were taken up by this mixture of isomers. On the other hand, the dendrimer having all azobenzene groups in the E form takes... 

Ueno et al. also prepared the b i s (2 - n ap h t h y I s u I fe n y 1) - y - CD series in which the naphthyl moieties are very limited in their movement because the linker between naphthalene and CD is only sulfur [37], All isomers of 12(AB), 13(AC), 14(AD), and 15(AE) exhibit only monomer fluorescence due to the rigid linker. It means that the two naphthalene moieties cannot take face-to-face orientation because of the limited flexibility. Although the excimer cannot be used for sensing molecules, Ueno et al. found that the monomer fluorescence intensity increases with increasing guest concentration. Thus, this modified CD series can be used as chemosensors of a different type. 

Moriwaki, F. Kaneko, H. Ueno, A. Osa, T. Hamada, F. and Murai, K. (1987) Excimer Formation and Induced-Fit Type of Complexation of P-Cyclodextrin Capped by Two Naphthyl Moieties, Bull Chem. Soc. Jpn. 60, 3619-3623. 

Disregarding this aspect, and since cyclam is an interesting core for constructing den-drimers because it can be easily functionalized and because despite its absence of spectroscopic properties, it can interact in such a way with dendrons as to modify their photophysical properties, the interaction of lanthanide ions with cy clam-based dendrimers has been investigated. The dendrimers are constmcted from the cyclam core fitted with four dimethoxyben-zene and eight naphthyl units (generation 1, fig. 81) second generation introduces a total of 12 dimethoxybenzene and 16 naphthyl moieties. Coordination to Lnm ions occurs in acetoni-trile/methylene chloride (Ln = Nd, Eu, Gd, Tb, and Dy), but no sensitized Ln-luminescence was observed (Saudan et al., 2004). Another example of a macrocycle-based dendrimer is discussed below in section 3.3.2. 

The introduction of a bulky, optically active amino function at C-2 of 4-phenyl-l-thiabutadiene and activation by the addition of AcCl prior to cycloaddition with Wphenylmaleimide, known to exhibit a high endo preference, results in the formation of two diastereomers. However, the exo product is the major component and indeed this diastereo-mer is the sole adduct when cyclopentene is used as the dienophile. Calculations point to a preference for exo addition from the same face of the molecule as the naphthyl moiety and this is supported by the observed R stereochemistry at the three chiral centers in the cyclopenta[A]dihydrothiopyran 434 (Scheme 140) <1996TL123>. 

Photochemical E —> Z isomerization produces a sterically strained state in which the methyl substituents are positioned in close proximity. The strain is released when the methyl groups and the naphthyl moieties switch their positions. This second step is followed by back-isomerization from the Z to the E form of the double bond and again steric hindrance provides an energetically unfavorable state which can reach an energetically more favorable state by a second flip of the sub-... 

However, if the nucleophiles have a low antibonding n MO, as in the case with the 1-naphthaleneselenate ion, the radical anion formed does not fragment because the odd electron is localized in the naphthyl moiety as a n radical anion. In this system only the substitution product 1-naphthyl-1-adamantyl selenide was formed in 50% yield122. 

On the other hand, the photostimulated reaction of 2-naphthylamide ions with iodoben-zene, p-iodoanisole or 1-iodonaphthalene gave mainly substitution at Q of the naphthyl moiety, affording amines 175 (45-63%) and traces of A-aryl-substitution product 176 (1-6%) (equation 1 19)224. 

Peroxidases are also active in the oxidation of naphthyl derivatives. In particular, when the substrates are 2-naphthols, the interesting derivatives 1,1 -dinaphthyl-2,2 -diols are formed [23] (Fig. 6.Id). In the presence of suitable substituents blocking the rotation of the naphthyl moieties, chiral binaphthyls can be obtained with enantiomeric enrichment [33, 34]. 

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