Ring compound nine-membered

Ab initio, semi-empirical, and molecular mechanics calculations have been used extensively in the study of nine-membered heterocycles. Theoretical studies of heteronines have centered on the question of their aromaticity, which was surveyed as a part of general heterocycles aromaticity study <2004CRV2777>. Another important aspect is the conformation of the nonconjugated compounds (see Section 14.10.4.3). Computational aspects of conformational behavior of saturated nine-membered rings and nine-membered rings containing one torsional constraint were the part of the review <1999MI(5)89>. 

The course of alkylation is also influenced by the steric arrangement of the enamine. 1-Pyrrolidino-l-cycloheptene gave approximately equal quantities of the C- and N-alkylated products in dioxane, while 1-pyrroli-dino-l-cyclooctene, and 1-pyrrolidino-l-cyclononene afforded N-alkylated products exclusively under similar eonditions (29). The reason for N alkylation in the eight- and nine-membered ring compounds is to be found in the conformation of these rings, which prevents full interaction of the unshared electrons on nitrogen with the n eleetrons of the double bond. 

Other advances include the construction of seven- and nine-membered rings via the analogous [4-1-3] and [6-1-3] cycloadditions with dienes and trienes respectively. Heterocycles, such as tetrahydrofurans and pyrrolidines, are accessible using carbonyl compounds and imines as substrates. The following discussion is organized around these recent discoveries. It serves to illustrate the versatility and the high degree of selectivity which are some of the distinctive features of the Pd-TMM chemistry. 

Bovio, B., Bonati, F. and Banditelli, G. (1984) X-ray crystal structure of tris[p-3,5-bis (trifluoromethyl) pyrazolato- N, N ] trigold(I), a compound containing an inorganic nine-membered ring. Inorganica Chimica Acta, 87, 25-33. 

Following their studies on the trapping of intermediates in the [5 + 2]-cycloaddition with CO, which led to the [5 + 2 + l]-process, the Wender group found that when related reactions were conducted with aryl alkynes under an atmosphere of CO, a novel four-component [5 + 2 + 1 + l]-product was observed.172 A VCP, an alkyne, and 2 equiv. of CO react to give the biaryl compounds shown (Scheme 78) via the formation of a nine-membered ring intermediate. 

The mesoionic compound 41 was further used in a reaction with dimethyl acetylene dicarboxylate (DMAD) to produce a nine-membered cycloadduct 44 which is formed by a reaction cascade of double addition of the alkyne and transannular ring opening of the intermediate 43 (Scheme 7) <20030BC978>. 

The properties of these compounds resemble those of the simple medium-ring lactams studied by Dunitz and Winkler (1975). A twisted conformation is observed for crystalline caprylolactam, where the preferred trans conformation cannot be properly accommodated in the nine-membered ring. 

A rationalization of the generally selective formation of the undesired C-16 -C-14 PREF relative stereochemistry on reaction of the chloro-imine-chloroindoline alkene 17a,b with vindoline (3) may be found in a preferred conformation, 25a or 25b, of the cationic intermediate 25, where the C-3 methylene group hinders approach to one face of the nine-mem-bered ring (Fig. 2). A conformationally more flexible nine-membered ring cationic intermediate 29a,b would be expected to be formed from the chloro derivative of a D-secocleavamine 30. From reaction of such a compound with vindoline (3), under the usual protic acid conditions for cou-... 

It has been shown that ruthenium carbene complex lb developed for olefin metathesis can catalyze RCM of enynes. Using this catalyst lb, five- to nine-membered ring compounds 3 are synthesized from enyne 2 (Scheme j) i Sa-iSc The reaction procedure for RCM of an enyne is very simple. A benzene solution of enyne 2b is stirred in the presence of 1 mol% of ruthenium carbene complex lb at room temperature (RT) under argon gas to give cyclic compound 3b having a diene moiety. 

The transannular interaction in the eight-membered (and also in nine-membered) ring amino ketones decreases the oxygen (170) exchange rate with water, as shown by 170 NMR, which also reveals an unusually shielded 170 chemical shift in such compounds (72HCA907). 

Planar nine-membered rings, as shown in Figure 2.67, represent an interesting group of complexes which have been widely studied. Compound [ ( = )3]... 

SAMPLE SOLUTION (a) The molecule has a tert-butyl group bonded to a nine-membered cycloalkane. It is tert-butylcyclononane. Alternatively, the tert-butyl group could be named systematically as a 1,1-dimethylethyl group, and the compound would then be named (1,1-dimethylethyl)cyclononane. (Parentheses are used when necessary to avoid ambiguity. In this case the parentheses alert the reader that the locants 1,1 refer to substituents on the alkyl group and not to ring positions.) ... 

Asymmetric epoxidation, dihydroxylation, aminohydroxylation, and aziridination reactions have been reviewed.62 The use of the Sharpless asymmetric epoxidation method for the desymmetrization of mesa compounds has been reviewed.63 The conformational flexibility of nine-membered ring allylic alcohols results in transepoxide stereochemistry from syn epoxidation using VO(acac)2-hydroperoxide systems in which the hydroxyl group still controls the facial stereoselectivity.64 The stereoselectivity of side-chain epoxidation of a series of 22-hydroxy-A23-sterols with C(19) side-chains incorporating allylic alcohols has been investigated, using m-CPBA or /-BuOOH in the presence of VO(acac)2 or Mo(CO)6-65 The erythro-threo distributions of the products were determined and the effect of substituents on the three positions of the double bond (gem to the OH or cis or trans at the remote carbon) partially rationalized by molecular modelling. 

Fig. 14.29. Preparation of an a-diazoketone (compound E) from a ketone (A) and subsequent Wolff rearrangement of the a-diazoketone. Initially, A is transformed to give the enolate B of its a-formyl derivative. In a Regitz diazo group transfer reaction, this will then be converted into the a-diazoketone E. Ring contraction via Wolff rearrangement occurs and the 10-membered cyclic diazoketone C rearranges in aqueous media to give the nine-membered ring carboxylic acid E via the ketene D.

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