Phenyl moiety

The high enantioselectivity observed was interpreted in terms of the face selectivity of the (Z)-enolate 59 (Scheme 1.20). The phenyl moiety is thought to stabilize the enolate through a n-n interaction and effectively shield its Re face such that the incoming ketone approaches preferentially from the Si face. 

Efremov and coworkers investigated the mass spectra of 18 methyl-substituted diphenyl (63)40 and substituted phenyl mesityl sulfones (64)41. The mass spectra of practically all the compounds showed by the rearrangement ions [M — OH]+, [M —H20]+ and [M — (H20 + OH)]+, the relative abundances of which depend on the position of the substituent in the phenyl moiety (ortho effect). It was also evident that in 63 the introduction of the first methyl substituent clearly decreases the contribution of the sulfone sulfinate isomerization (equation 30) to their fragmentation whereas the further substitution had little or no effect on the isomerization process in both 6340 and 6441. 

Recently we pointed ont that the cyclopentadiene having phenyl moiety at the 5-position is the diene of omo- phenyl moiety can mediate orbital... 

Mataka ascribed the selectivity to tt/tt interaction between the phenyl moiety of dienophiles and most closely stacked aromatic part of the anthracenophanes 96 and 97, while again Nishio stated that the selectivity is dne to the attractive CH/tt interaction [53] (Scheme 48). 

Subsequently, these catalysts were evaluated in the enantioselective desymmetri-sation of achiral trienes, and three distinct trends in catalyst selectivity were found. Firstly, catalysts 56a-b with two phenyl moieties on the backbone of the A -heterocycle exhibited higher enantioselectivity than those with a fused cyclohexyl group as the backbone 55a-b. Secondly, mono-ort/io-substituted aryl side chains induced greater enantioselectivity than symmetrical mesityl wing tips. Thirdly, changing the halide ligands from Cl to I" increased the enantioselectivity. As a result, catalyst 56b turned out to be the most effective. For example, 56b in the presence of Nal was able to promote the desymmetrisation of 57 to give chiral dihydrofuran 58 in up to 82% conversion and 90% ee (Scheme 3.3). 

Generalization tests indicated that a number of compounds were able to substitute for PCP (table 1). Ketamine and tiletamine, which are structurally similar to PCP, produced dose-dependent effects mimicking PCP. These compounds are interesting examples of the structural requirements of molecules for PCP-mimetic activity, demonstrating that neither the piperidine nor the phenyl moieties are absolutely necessary for activity. 

IkB kinase-p is a key regulatory enzyme in the NF-kB pathway, and inhibition of this enzyme has the potential for yielding treatments for inflammatory and autoimmune diseases. Morwick et al. [53] report on the optimization of a pM IKKp inhibitor with low aqueous solubility, moderate human liver microsome stability, and inhibition of several CYPs (3A4, 2C9, 1A2) with pM potencies. Modulation of the thiophene core (other thiophene isomer, pyrimidine and oxazole) produces compounds of similar potency to the hit. Fusing the 5-phenyl moiety to the thiophene to form a thieno[2,3-b]pyridine core increases aqueous solubility of the series as well as reduces the CYP liability. While the optimized compound still shows pM IKK(S potency, the aqueous solubility, HLM stability and CYP profiles are much improved. A pharmacophore model was generated that enabled scaffold hopping to yield this new chemotype (Scheme 7). 

Replacement of methine by nitrogen, i.e., replacement of a phenyl moiety by pyridine, is consistent with biological activity in quite a few structural-... 

X-ray crystallographic analysis of the crystalline [bicumene, NO+] charge-transfer salt confirms that the charge-transfer color arises from a close approach of NO+ to the centroid of the phenyl moiety (see Fig. 10) with a non-bonded contact to an aromatic carbon of 2.63 A.194 The orange solution of bicumene bleaches slowly over a long period in a thermal reaction at room temperature (in the dark) or rapidly via irradiation of the CT band at low temperature. In both cases, l,l,3-trimethyl-3-phenylindane is obtained as the principal organic product (equation 63). 

Fig. 10 ORTEP diagram showing the complexation of nitrosonium cation with a single phenyl moiety of bicumene. Reproduced with permission from Ref. 194.

Figure 3.43 Expanded NOESY spectra (CDC13, 30°C) of the mixtures of (a) (R)-41a and 23ao and (b) (S)-41a and 23ao (molar ratio 1 2) in region between aromatic protons (41a and 23ao) and methyl protons on phenyl moiety of 23ao. (Reprinted with permission from Ref. 209. Copyright 1996 by the American Chemical Society.)...

From the examination of structure-activity relationships, it has been concluded that a phenyl moiety at C-6 as well as a 4-hydroxypiperidine side-chain attached to C-3 of the pyridazine system is essential for anticonvulsant activity in this class of compounds [184], Compounds (54) and (55) have been found to have similar anticonvulsant profiles in animals (mice, rats and baboons) [165, and literature cited therein] and to represent potent broad-spectrum antiepileptic drugs. Their potency with regard to antagonizing seizures (induced by electro-shock or various chemicals) has been compared with standard anticonvulsants like carbamazepine and phenobarbitone [185, 186], A quantitative electroencephalographic analysis of (55) has been published [187]. From in vitro studies it has been concluded that the anticonvulsant activities of these compounds are not mediated by an enhancement of GABAergic transmission or by an interaction with benzodiazepine receptor sites [ 165,186,187], On the other hand, in vivo experiments showed that (54), at anticonvulsant doses, increases the affinity of flunitrazepam for its central receptor site [ 186], Investigations of (54) and (55) in a behavioural test predictive of antianxiety activity revealed a marked difference in the pharmacological profiles of these structurally closely related compounds the dichloro compound SR 41378 (55) has also been found to possess anxiolytic (anticonflict) properties [165],... 

As a typical example of a 6-heteroarylsubstituted dihydropyridazinone exhibiting antithrombotic activity motapizone, NAT 05-239 (63) (CAS 90697-57-7) may serve [96], Compound CCI 17810 (64) (CAS 76283-03-9) bearing a substituted phenyl moiety at C-6 of the pyridazine system has been shown to inhibit potently in vitro human platelet aggregation (induced by collagen, ADP, thrombin or arachidonic acid) with EC50 values in the range of 0.5-10/rg/ml [245], ... 

Rd stands for the usual substituents for diazo components (see, for instance, Sec. 2.6.1). However, it may also comprise additional carbonamide groups, connected via phenyl moieties. In commercially important pigments, A commonly represents a phenylene or a diphenylene group, and n is any number between 1 and 3. This general structure also covers orange and brown pigments. 

In industrially interesting pigments, X usually stands for O or N-R, and R represents H, CH3, or possibly a substituted phenyl moiety. The phenyl ring may... 

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