Fragmentation of diastereoisomers

The decalin shown below can undergo ring expansion. However, this ring expansion is fairly complex because the starting material has three stereogenic centres (*), and hence can exist as four diastereoisomers: two trans-decalins and two cis-decalins; the alkoxide can exist in both the axial and equatorial position. The product is a ten-membered ring which contains a double bond. This double bond can be either cis or trans.

One of the four diastereoisomers cannot fragment, whereas the other three can. Two of them give a
trans double bond and the other a cis one.

Click the diastereoisomers shown below to see which product is formed:

(Can you guess which diastereoisomer does not undergo ring expansion and why?)

NOTE: The mesylate leaving group was used in place of tosylate to enable the calculations to run more smoothly

M. A. Drahl, M. Manpadi and L. J. Williams, Angew. Chemie – Int. Ed., 2013, 52, 11222–11251.

 

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