Rearrangement, Oxidation, Reduction, Simple Functionalizations

Rearrangement, Oxidation, Reduction, Simple Functionalizations.—(+)- -Pinene was converted into the rare (+)-fl-pinene (optical yield 90%) via conversion into 

Nesmeyanov, I. V. Shchirina-Eingoru, G. M. Khvostik, V. N. Sokoloy, and I. I. Krits-kaya, Izv. Akad. Nauk SSSR, Ser. Khim., 1979, 2826. 

Photo-oxygenation of a-pinene in MeCN-HaO differed from that in aprotic media the main hydroperoxide was the same but it was accompanied by (218).546 Similar reaction of the p-isomer in the presence of metal oxides gave myrtenol, myrtenal, nopinone, and pinocarvone.547 a-Pinene was reduced to m-pinane (96% stereoselective) over Ru,648 and electrochemical reduction of 2,4-dibromo-pinocamphone gave a variety of products devoid of Br.549 Hydroboration of amino-and azido-pinanes550 and the conversion of a-pinene into 2-hydroxy-3-amino- and 3-hydroxy-5-amino-pinanes have been reported.551-553 syn-Addition of 2HC1 to the 

The cyclic ether (219) was converted into (220), which underwent rearrangement to (221) in a manner analogous to the celebrated norcaradiene ring-walk stereochemical analysis of the rearrangement indicated predominant inversion of configuration for both the photolytic and thermal processes and so symmetry considerations of the Woodward-Hoffman type may not be relevant to these (or at least the thermal) processes.559 Esters of pinocarveol were converted into myrtenyl compounds by CuOAc.560 cis- and rrans-Verbenyl and verbanyl acetates,561 562 related compounds563 and 2-methylverbanone564 have been synthesized for evaluation as attractants for cockroaches. 

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