1- Adamantanol synthesis

Boyle, T. J. Pearson, A. T. Schwartz, R. W. 1994. Synthesis and characterization of Group IV metal adamantanol alkoxides as potential PZT precursors. Ceram. Trans. 43 79-87. 

Synthesis of 1-Adamantanol from Adamantane through Regioselective Hydroxyiation by Streptomyces griseoplanus Cells... 

The procedure is an approach for the synthesis of 1-adamantanol from adamantane by a green bioprocess. 

Clearly, many extensions of these rr-route cyclizations should be possible for the convenient synthesis of a variety of 2,4-disubstituted adamantanes. An illustrative example is provided by the rearrangement of the alcohol 91 to 2,2-dime-thyl-4-adamantanol (Eq. (75))278>. 

Although the functionalization of unactivated C—H bonds by intramolecular nitrene insertion has been aj Iied to the synthesis of diterpene alkaloids and in the modification of steroids as described below, it has also been used to good effect in simpler systems. For example, 1-adamantyl azidoformate, readily prepared from 1-adamantanol, gives the oxazolidinone (17) on irradiation in cyclohexane by in-... 

Protoadamantanone is a versatile intermediate for the synthesis of not only protoadamantane derivatives,but also 1,2- and 2,4-disubstituted adamantanes, 2-substituted noradamantanes, and 4(5)-substituted 4-homoprotoadamantanes. 4-Protoadamantanone has been prepared by the nitrous acid deamination of 2-amino-l-adamantanol (77%), by aprotic diazo-tization of endo-7-aminomethylbicyclo[3.3.1]nonan-3-one in benzene with an equivalent amount of acetic acid (67%), and by thermolysis of 1-adamantyl hypohalites followed by base-promoted cyclization of the resulting halo ketones (32-37%).In spite of low and erratic yields, the last reaction sequence has provided the most convenient route to the protoadamantanes, since the other two approaches require lengthy syntheses of the starting materials. 

Strecker synthesis. The 3,3 -disubstituted BINOL 1 is used in promoting addition of Me3SiCN to A -tosylketimines. Adding one equivalent of 1-adamantanol enhances reaction rates and enantioselectivity. ... 

Trialkylboranes give trialkylcarbinols on Hilmann carbonylation followed by oxidation . One of the most effective applications of this reaction in organic synthesis is the conversion of 1-boraadamantanes to the corresponding 1-adamantanols (Scheme 45) <76IZV2302>. 

Esters of 2-iodoxybenzoic acid (IBX-esters) 489 have been prepared by the hypochlorite oxidation of the readily available 2-iodobenzoate esters 488 (Scheme 2.139) and isolated in the form of stable microcrystalline solids [657,658], This procedure has been used for the synthesis of IBX-esters 489 derived from various types of alcohols, such as primary, secondary and tertiary alcohols, adamantanols, optically active menthols and borneol. Single-crystal X-ray data on products 489 revealed a pseudo-benziodoxole stmcture in which the intramolecular L--0 secondary bonds partially replace the intermolecular I - O secondary bonds, disrupting the polymeric structure characteristic of Phl02 and other previously reported iodylarenes [658], This stmctural feature substantially increases the solubility of these compounds in comparison to other iodine(V) reagents and affects their oxidizing reactivity. 

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