Cycloalkanol 1-

Tertiary alcohols are usually degraded unselectively by strong oxidants. Anhydrous chromium trioxide leads to oxidative ring opening of tertiary cycloalkanols (L.F. Fieser, 1948). 

Cycloahphatic amine synthesis routes may be described as distinct synthetic methods, though practice often combines, or hybridi2es, the steps that occur amination of cycloalkanols, reductive amination of cycHc ketones, ring reduction of cycloalkenylarnines, nitrile addition to ahcycHc carbocations, reduction of cyanocycloalkanes to aminomethylcycloalkanes, and reduction of nitrocycloalkanes or cycHc ketoximes. 

The original Demjanov reaction is the conversion of an aminomethyl-cycloalkane into a cycloalkanol consisting of a carbocyclic ring that is expanded by one carbon center e.g. the reaction of aminomethylcyclohexane 8 with nitrous acid leads to formation of cycloheptanol 9 ... 

Fig. 4. Plots of log 1 /Kd vs. log Pe for complexes of a-cyclodextrin with branched alkanols (O) and cycloalkanols ( ). The solid line was given by the plots for an a-cyclodextrin-1-alkanol system. Numbers shown refer to the numbers in the first column of Table 2. Reproduced with permission from the Chemical Society of Japan...

Birman VB, Li X (2008) Homobenzotetramisole an effective catalyst for kinetic resolution of aryl-cycloalkanols. Org Lett 10 1115-1118... 

In the reaction with epoxides, y-hydroxysulfones are obtained " . For example, Kondo and coworkers synthesized various (5-lactols 226 by treating sulfone acetals 225 with terminal epoxides as shown below. Dilithiated phenylsulfonylmethylene reacted with haloepoxide and afforded 3-(phenylsulfonyl)cycloalkanols Treatment of y,i5-epoxysulfones 227 and 229 with n-butyllithium resulted in cyclization to form cyclopropane derivatives 228 and bicyclobutane 230, respectively . ... 

Various non-conjugated diene aldehydes react with Et3SiH/Ni(cod)2/PPh3 to give O-triethylsilylated cycloalkanols in low to high yields. Acyclic dienes can lead to the silylated cycloalkanols in moderate yields with the proper catalyst (Eq. 188).348 Bicyclic systems are also generated by this methodology (Eq. 189).349... 

Phenylthio)carbenoids 26 possessing different chain lengths (Scheme 12, n = 1,2, 3), namely, 4-, 5-, and 6-oxidoalkyl(phenylthio)carbenes (Table 6, entries 1, 7 and 8), undergo similar regioselective cyclization reactions to give 2-(phenylthio)cycloalkanols 27. 

Lautens and Chiu123 reported a reductive ring opening of oxabicyclo[/z.2.1]alkenes 93 using DIBAL in the presence of bis(cyclooctadiene)nickel to give the racemic cycloalkanols (Scheme 10). 

Although terminal acetylenes themselves do not form stable titanium—acetylene complexes upon reaction with 1, the reaction with terminal alkynes having a keto group at the 5- or y-position induces an intramolecular cyclization, apparently via the above titanium-acetylene complex to afford the four- and five-membered cycloalkanols, as shown in Eq. 9.6 [28]. 

The derivatives 24 were synthesised by the acylation of trans-2-aminocy-clopentanol (n=l) or frans-2-aminocyclohexanol (n=2) with 3,3-ethylene-dioxydodecanoic acid in the presence of EDC, DMAP and DIPEA followed by acidolysis with THF in DCM. The cycloalkanone analogues 25 were obtained by Swern oxidation of the corresponding cycloalkanols 24 (Scheme 10). 

Interestingly, cyclopentane and cyclohexane derivatives, which contain one or two hydroxyl, carbonyl, or carboxyl groups, degrade more readily in the environment than do their parent compounds. In fact, microorganisms capable of degrading of cycloalkanols and cycloalkanones are ubiquitous in environmental samples. 

Data are available (71) on the influence of ring size upon the rate of dehydration of Cj-Cg cycloalkanols on alumina they will be discussed in Section V,A,1, where they are summarized, together with other data concerning the reactivity of cyclic compounds in various reactions, in Table V. Here let it suffice to state that the reactivity pattern in dehydration fit the general rules known from noncatalytic chemistry well. 

Intensive studies concerning the photoreductive cyclization of distinct ketones and aldehydes are made by Cossy et al. [170], They describe how bicyclic tertiary cycloalkanols 173 and 174 can be prepared from, s-un-saturated ketones 172 in good yields, initiated by photoinduced electron transfer from triethylamine in acetonitrile or by photoionization in pure hexamethyl-phosphoric triamide (HMPA) [171, 172], The reaction is stereo-, chemo- and... 

Recently, Corma et al. have patented a process of oxidizing cycloalkane with molecular oxygen to produce cycloalkanol and/or cycloalkanone in the presence of hydrotalcite-intercalated heteropoly anion [Co MnCo (H20)039] (M = W or Mo), which comprised one cobalt as a central atom and another as a substitute of a W=0 fragment in the Keggin structure [98]. At 130 °C and 0.5 MPa, 64 and 24% selectivity to cyclohexanone and cyclohexanol, respectively, was achieved at cyclohexane conversion about 5%. This catalytic system could be of practical importance provided a true heterogeneous nature of catalysis and good catalyst recyclability had been proved. Unfortunately, this information was lacking in [98]. 

Reduction of cycloalkane-condensed 2-phenyl-5,6-dihydro-4//-l,3-benzoxazines 144 with lithium aluminium hydride (LAH) afforded A -benzyl-substituted 2-(aminomethyl)cycloalkanols 145 in a reductive ring opening via the ring-chain tautomeric tetrahydro-l,3-oxazine intermediates. Catalytic reduction of 1,3-oxazines 144 under mild conditions in the presence of palladium-on-carbon catalyst similarly resulted in formation of the A -benzyl-1,3-amino alcohols 145. When the catalytic reduction was performed at elevated temperature at hydrogen pressure of 7.1 MPa, the N-unsubstituted 2-(aminomethyl)cycloalkanols 146 were formed in good yields (Scheme 22) <1998SC2303>. 

R. Tsang and B. Fraser-Reid, Surprisingly efficient intramolecular addition of carbon radicals to carbonyl groups A ready route to cycloalkanols, J. Am Chem. Soc. 108 8102 (1986). 

Table 4.24. 13C Chemical Shifts of Representative Cycloalkanols [210, 268], Norborna-nols [229] and Hydroxydecalins [273] (< - in ppm).

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