We started our study with the multigram preparation of sultams 1ac according to the modified literature method. The key step in their synthesis was the ring-closing metathesis reaction of homologous dienes 3 (Scheme 2, A). These intermediates were synthesized by sulfonylation of allyl-(2a), homoallyl-(2b), and benzyl homoallyl (2c) amine with 2-chloroethanesulfonyl chloride in the presence of Et3N as a base. The reaction was accompanied by elimination and gave dienes 3a-c in high yields (92-99%). The Grubbs II catalyst-mediated metathesis provided sultams 1a (92% yield, 91% over two steps), 1b (89% yield, 85% over two steps), and 1c (86% yield, 79% over two steps). Using an improved catalytic system (Grubbs II vs Grubbs I catalyst used previously ) ensured the scalability of the method: compounds 1a-c were obtained on up to 113 g scale. Compounds 1a and 1b were subjected to the N-protection with Boc2O to give γ-sultams 1d and 1e (both obtained on ca. 20-g scale in 90% yield). In addition to that, parent γ-sultam 1a reacted with Br2 to provide addition product 5 (Scheme 2, B). The subsequent treatment of intermediate 5 with Et3N gave the product of the regioselective eliminationsultam 1f (168 mg, 85% yield). With the multigram quantities of sultams 1a-e in hands, we have evaluated their reactivity towards various 1,3-dipolar compounds in the [3 + 2] cycloaddition (Scheme 3). It was found that nitrone 6a (A), nitrile oxide generated from chloroxime 7a (B), as well as azomethine ylide generated from precursor 8 (C) provided corresponding cycloadduct 9-11 in moderate to good yields (20-88%). Azomethine ylide generated from isatin and N-methylglycine (sarcosine) reacted with -sultams 1a and 1d, but the corresponding cycloadducts 12a and 12b were obtained in 16% and 17% yield, respectively (D). The relative stereochemistry of all obtained cycloadducts was confirmed by 2D NMR experiments (see the Supporting Information for more details). Other methods for azomethine ylide generation, i.e., the decarboxylative condensation of secondary α-amino acids such as proline (E) or sarcosine (F) with benzaldehyde, action of various transition metal catalysts on methyl 2-(benzylideneamino)acetate (G), or using 1-methylpyridin-1-ium-3-olate (H) were not fruitful. Likewise, a carbonyl ylide precursor (I) and ethyl allenecarboxylate -Bu3P adduct (K) failed to provide the target bicyclic sultams. In experiments (H) and (I), complex mixtures of unidentified products were formed, likely due to the polymerization of the starting materials; in all other experiments, starting sultams 1a-e were recovered. Finally, an attempted [3 + 2] cycloaddition with aliphatic azides (J) gave the corresponding monocyclic 1,2,3-triazoles 14 in 76-82% yield, likely via decomposition of initially formed bicyclic cycloadducts 13 and/or their regioisomers.