We have found that the reaction of (+)-10-camphorsulfonylchloride (I) with I2NEt 3 in CH2C12 at 0 ~ affords a,13-unsaturated atdehyde (2) in 50% yield, gemDiiodo-derivative (3) (-16%) and iodoaminals (4) and (5) (-7%) are minor products in this reaction. The structure of aldehyde 2 is confirmed by spectral data and chemical transformations. In particular, oxidative cleavage of the double bond in 2 with an OsO4(cat.)--Na[O4 t system results in the known oxoaldehyde (6). z,3 Studies of the mechanism and synthetic potential of this new reaction are now in progress in our laboratory.

Sterical loading, topology, and the character of the organic molecule functionalization sometimes lead to the "uncommon" course of typical reactions with its participation. One of such compounds is epoxycyclohexanone I that we have recently described [1].Our attempts to convert it into hydroxycyclohexanone II by ozonolysis under the conditions of Criegee rearrangement [2, 3] resulted only in diketone III [1] inert with respect to m-chloroperbenzoic acid. We also failed to perform the oxidative cleavage of epoxyalcohol IV by treating with HIO 4 , we obtained only diol V. At the reduction of epoxyalcohol IV with LiAlH 4 alongside the expected diol VI we isolated regioisomeric diols VII and O O O OH O O O O O 3 I II III HO O IV NaBH 4 HO OH V HIO 4 THF _ H 2 O m-ClC 6 H 4 CO 3 H VIII. Usually the reduction with LiAlH 4 of trisubstituted epoxides provides a tertiary alcohol. The assignment of stereoisomeric diols VII and VIII was done based on the characteristic doublets of H 3 in the 1 H NMR spectra. Whereas for 2,3-trans-isomer VII J 3,2 is 11.2 Hz [δ(H 3 ) 3.30 ppm], in the isomer VIII J 3,2 is 5.2 Hz [δ(H 3 ) 3.51 ppm] (analogous examples have been described in [4]). For further identifi cation diol VIII was converted into diacetate IX. HO OH VI, 33% IV HO OH HO VII, 27% VIII, 7% OH AcO OAc Ac 2 O _ Py IX + LiAlH 4 THF, Δ +Thus except for the reduction of the epoxyketone I with sodium borohydride into alcohol IV the other reactions of these compounds proceeded by unexpected routes or with the partial formation of abnormal products.(1R,3R,5S)-4,4-Dimethyl-5-isopropenyl-2-methylidenecyclohexane-1,3-diol (V). To a solution of 0.08 g (0.41 mmol) of compound IV in 5 ml of the mixture

Starting with R-(-)-carvone hydrochloride a synthesis was developed of the key chiral block for the epothilones gem-dimethylcyclopropane analog.

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6-Hydroxy derivatives of R-(-)-carvone and 7,8-epoxycarvone were synthesized and subjected to oxidative ring cleavage by the action of lead tetraacetate. These reactions followed different patterns, depending on the substrate structure.