L- -undecane

Problem 9.36 Draw formulas for (o) isopropylcyclopentane, b) c -l,3-dimethylcyclooctane, (c) bicyclo[4.4. l]undecane, (d) rrarw-l-propyl-4-butylcyclohexane. 

Earlier examples of copper(I)-photocatalyzed cycloalkene cyclodimerizations have been summarized in Houben-Weyl, Vol. 4/5a, pp 280-292 as was the copper(I) chloride photocata-lyzed isomerization of cycloocta-1,5-diene to tricyclo[3.3.0.02 6]octane (see Houben-Weyl, Vol. 4/5 a, p 231). This same reaction has recently been used for the preparation of 4-oxatctra-cyclo[6.3.0.02,(,.07,1 L]undecanes.10... 

With peroxybenzoic acid or bis(trimethylsilyl)peroxide, II can be oxidized to cis-l,6-dimethyl-II-oxa-l,6-disila-[4,4,l]-undecane (III). This compound can be obtained only in the cis form since in the trans form the ring straining is too great... 

Michael addition of the dianions derived from -dicarbonyl compounds facilitated yet another annulation - Michael addition of a dianion then intramolecular aldol condensation (Scheme 6.89) [112]. Complexation of ATPH with trans-chal-cone (112) in CH2CI2 at -78 °C, followed by treatment with the dianion of methyl acetoacetate gave, after quenching with aqueous HCl, bicyclic product 113 in a nearly quantitative yield. This system can be used for elaboration of the bicyclo [3,5,l]undecane ring system in 114, as can be found in the backbones of terpenoids and the taxol family. 

This account follows the same scheme as last year s. Synthesis is discussed in sections according to reaction type and is followed by a brief consideration of miscellaneous reactions. The emphasis on synthetic studies continues but the increasing interest in the pharmacology of many of the novel systems is not discussed. Recent topics include the analgesic activity of l-azabicyclo[4,4,l]-undecanes, 3-azabicyclo[3,2,l]octanes, 3-azabicyclo[3,2,2]nonanes, 9-azabicyclo[3,3,l]nonanes, and substituted quinuclidines. ... 

The keto-epoxide (273) can be cyclized with formic acid or KOBu -BuOH to give derivatives of bicyclo[4,4,0]decan-2-on-7-ol, but with aluminium trichloride or basic alumina gives the products (273a) and (273b), and related products with the ll-oxabicyclo[5,3,l]undecane skeleton. ... 

Numbering of (XXII) offers no difficulty, and the name is ll,ll-dimethylbicyclo[4,4,l]undecane. 

Azabicyclo[2.1.0]pentane-3-carboxylic acid antimicrobial activity, 7, 346 l-Azabicyclo[3.3.3]undecane — see Manxine 1 - Aza-2-boracyclohexane, 1 -methyl-synthesis, 1, 647... 

Undecan-l-ol [112-42-5] M 172.3, m 16.5 . Purified by repeated fractional crystn from its melt or by distn in a vacuum. 

Bohlmann et al. (118-121) observed that an infrared absorption band between 2700-2800 cm is characteristic of a piperidine derivative possessing at least two axial carbon-hydrogen bonds in antiperiplanar position to the free-electron pair on the nitrogen atom. The possibility of forming an enamine by dehydrogenation can be determined by this test. Compounds which do not fulfill this condition cannot usually be dehydrogenated (50, 122,123). Thus, for example, yohimbine can be dehydrogenated by mercuric acetate,whereas reserpine or pseudoyohimbine do not react (124). The quinolizidine (125) enamines (Scheme 4), l-azabicyclo(4,3,0)-nonane, l-azabicyclo(5,3,0)decane, l-azabicyclo(5,4,0)undecane, and l-azabicyclo(5,5,0)dodecane have been prepared in this manner (112,126). 

Figure 15.11 (a) Total ion clnomatogram of a Grob test mixture obtained on an Rtx-1701 column, and (b) re-injection of the entire clnomatogram on to an Rtx-5 column. Peak identification is as follows a, 2,3-butanediol b, decane c, undecane d, 1-octanol e, nonanal f, 2,6-dimethylphenol g, 2-ethylhexanoic acid h, 2,6-dimethylaniline i, decanoic acid methyl ester ], dicyclohexylamine k, undecanoic acid, methyl ester 1, dodecanoic acid, methyl ester. Adapted from Journal of High Resolution Chromatography, 21, M. J. Tomlinson and C. L. Wilkins, Evaluation of a semi-automated multidimensional gas chromatography-infrared-mass specti ometry system for initant analysis , pp. 347-354, 1998, with permission from Wiley-VCH. 

The tricarbonylchromium complex 6 of methyl 1/f-azepine-l-carboxylate undergoes photoin-duced [6 + 4] 7t-cycloadditions with dienes, e.g. 7, to give, after decomplexation with oxygen, azabicyclo[4.4.1]undecanes, e.g. 8, in high yields.276... 

Spiroketals based upon such structures as l,7-dioxaspiro[5.5]undecane (18), occur frequently in natural products. Accordingly, an extensive amount of literature relates to the isolation and total synthesis of this type of compound. This literature was reviewed104 in 1989. The authors of Ref. 104 listed three factors that influence conformational preferences in these systems. They are (7) steric influences, (2) anomeric and related effects, and (3) intramolecular hydrogen bonding and other chelation effects. 

FIGURE 5 Gas chromatogram of degradation products of a linear polymer prepared from 3,9-bis-(ethylidene-2,4,8,10-tetraoxaspiro[5,5]undecane) and l,6-hexanediol. (From Ref. 16.)... 

A ketene acetal-terminated prepolymer was first prepared from 2 eq of the diketene acetal 3,9-bis(ethylidene-2,4,8,10-tetraoxaspiro-[5,5]undecane) and 1 eq of the diol 3-raethyl-l,5-pentanediol and. then 30 wt% levonorgestrel, 7 wt% Mg(OH)2j and a 30 mole% excess of 1,2,6-hexanetriol mixed into the prepolymer. This mixture was then extruded into rods and cured. Erosion and drug release from these devices was studied by implanting the rod-shaped devices subcutaneously into rabbits, explanting at various time intervals, and measuring weight loss and residual drug (15). 

---