Cyclopentanols, 2-amino

The reaction of nitrous acid with the amino group of the /3-amino alcohol—e.g. 1-aminomethyl-cyclopentanol 1—leads to formation of the nitrosamine 4, from which, through protonation and subsequent loss of water, a diazonium ion species 5 is formed " —similar to a diazotization reaction ... 

The oxidation of cyclic 2-amino alcohols has been studied.88 In the 2-amino-cyclopentanol series, the ds form was oxidized four times as fast as the trans but, in the 2-amino-cyclohexanol series, the ds form reacted slightly more slowly than did the tram. 

Substrates include benzyl (2 g) and cinnamyl (2.7 g) alcohols to acids cyclopentanol (1 g), benzhydrol (3.9 g), benzoin (4 g), pantolactone (2.6 g) to ketones (RuCy TCCA/( Bu N)Br/aq. Kj(C03)/CH3CN) (Fig. 2.14) [25] [[2-[2-hydroxypropyl) amino]-l,2-dioxoethyl]amino]acetic acid ethyl ester (6.21 kg) to [(l,2-dioxo-2-oxopropyl)amino]ethyl)amino] acetic acid ethyl ester, part of the industrial-scale synthesis of thrombin inhibitor (RuCyaq. Na(BrOj)/CH3CN) [166] (H-)-dihydroc-holesterol (8 g) to cholest-3-one (RuO /aq. K(10 )/(BTEAC)/CHCl3) [308] ... 

In contrast to the results of Kovar et at., McCasland and Smith found that ci5-2-amino-cyclopentanol is oxidised more rapidly than the trans- isomer. Bar-low et al. determined the second-order rate coefficients at pH 4.0 (acetate buffer) and 25 °C for a series of amino sugars derived from the eight isomeric methyl-4,6-0-benzylidene-a-D-glycosides (VII)... 

The di-Grignard method has also been applied to reactions of disubstituted amino [41,42], phenoxy, and phenylthio esters [42] to provide difunctional cycloalkanols examples include the conversion of esters 53 to cyclopentanols 54 [Eq. (20) 42]. Similarly, lactones can be converted to diols as in the formation of cyclopentanol 56 from lactone 55 [Eq. (21) 43]. 

The stereochemical outcome of the rearrangement of iminium ions derived from /ra/ .v-2-amino-l-(l-arylvinyl)cyclopentanols (e.g., 11) indicates that out of the topographically different pathways only transition state 14 accounts for the preferred formation of 101134. 

Dimethylaluminium amides of ( )-a-methylamine facilitated preparation of trans-2-amino-cyclohexanol and -cyclopentanol. After reaction with the appropriate cycloalkene oxide, separation of the... 

Conjugation with amino acids, preferentially isoleucine, of the non-me-tabolized dihydrojasmonic acid and jasmonic acid, their 11-OH and 12-OH metabolites and the cyclopentanol metabolites. 

A mixture of l-(a-iminocyclohexylmethyl)cyclopentanol and 96%-formic acid heated 5 hrs. at 100° in an oil bath crude 2-amino-2-cyclohexylcyclohexa-none. Y 50-60%. I. Elphimoff-Felkin, Bl. 1962, 653. 

Amino-sec-alcohols. An aq. soln. of 2,5-bis(dimethylaminomethyl)cyclopenta-none dihydrochloride added dropwise during 20 min. to a stirred cooled aq. soln. of NaBH4, stirred 2 hrs., decomposed with excess NaOH-soln., and the product isolated as the dihydrochloride 2,5-bis(dimethylaminomethyl)-cyclopentanol dihydrochloride. Y 80%. F. F. Blicke and F. J. McCarty, J. Org. Chem. 24, 1069 (1959). 

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