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Distinguish the original thiirane sulfur $S_o$ from the sulfur $S_n$ supplied by thiocyanate. sulfur attack by ${}^{-}{\mathrm{S}}_{\mathrm{n}}-\mathrm{C}\equiv \mathrm{N}$ at one thiirane carbon opens its C–$S_o$ bond with inversion. This produces a thiolate at the neighbouring carbon and a C–$S_n$–CN group at the attacked carbon. The OH-bearing remote carbon is unaffected.

The original thiolate $S_o^{-}$ now attacks the nitrile carbon intramolecularly. Shift one C≡N pi pair onto nitrogen. The resulting cyclic imidodithiocarbonate has the five-membered sequence ring carbon–$S_o$–C(=N${}^{-}$)–$S_n$–adjacent ring carbon; its two carbon atoms are also part of the original six-membered carbocycle, exactly giving the hinted bicyclic intermediate.

Collapse can reform C≡N while breaking the nitrile-carbon–$S_n$ bond. This transfers the CN group to $S_o$ and generates $S_n^{-}$ as the thiolate on the other ring carbon. That thiolate attacks the remaining C–$S_o$ bond from the back, expelling ${}^{-}{\mathrm{S}}_{\mathrm{o}}-\mathrm{C}\equiv \mathrm{N}$ and reclosing the thiirane. Each thiirane carbon has undergone one inversion, so the new sulfur bridge lies on the opposite face; the OH configuration is retained. The thiocyanate sulfur has entered the ring and the original ring sulfur has left as thiocyanate. This atom-labelled exchange mechanism explains how the same elemental formula can conceal sulfur replacement; isotope labelling would be needed to test that exchange experimentally. A single epimerization at the OH carbon would give the wrong stereochemical outcome.

At 400 MHz, a separation $\Delta \delta$ in ppm corresponds to $J=400\Delta \delta$ Hz. The two multiplets near 5.10 and 4.47 ppm each have a quoted separation of 0.02 ppm, giving $J\simeq 8$ Hz. The multiplets near 4.625 and 3.865 ppm each have separation 0.01 ppm, giving $J\simeq 4$ Hz. These are approximate values from the rounded peak labels.

The fused unsaturated/aromatic framework restricts the five-membered ring, as in the comparison in (a). Assign the larger coupling to cis and the smaller to trans. Matching equal couplings and integrals pairs the 5.10/4.47 signals with one another, and the 4.625/3.865 signals with one another. The integral ratio isWith an achiral substrate and achiral catalytic environment, each diastereomer is expected as a racemic enantiomeric pair: cis $(2R,3S)/(2S,3R)$ and trans $(2R,3R)/(2S,3S)$. The reported spectrum requires both diastereomers; the reagent label alone cannot override that evidence. Their ratio does not establish whether the selectivity arose in the initial surface addition or after product epimerization.

The five-membered enone-like carbon framework can be obtained by an intramolecular aldol condensation ofEnolization at an internal methylene next to one ketone followed by attack on the opposite ketone closes a five-membered ring. dehydration leaves one acetyl group attached to one alkene carbon and one methyl group on the other. The two nitrile-bearing carbons remain adjacent and their original cis relationship is retained if epimerization is avoided.

Now reverse a reductive ozonolysis: the diketone arises by opening a six-membered cyclohexene whose alkene carbons each carry Me. That cyclohexene is the Diels-Alder reaction product of 2,3-dimethylbuta-1,3-diene and maleonitrile. The latter is the supplied cis dinitrile. The stereospecificity of the cycloaddition puts the two CN groups on the same face.

Thus the forward plan is Diels–Alder addition, reductive ozonolysis, then five-membered aldol ring closure and dehydration. Use a reductive ozone work-up that stops at the diketone. During the final step, avoid prolonged strongly basic heating because the carbons bearing CN can be deprotonated and epimerized. Achiral reagents give the racemic pair with the required cis relationship; resolution would be necessary if only the depicted enantiomer were required. The diene supplies six carbons and maleonitrile supplies four, accounting for all ten carbons without an unexplained carbon deletion.