Facile Access to Bicyclic Sultams with Methyl 1‐Sulfonylcyclopropane‐1‐carboxylate Moieties

Abstract

N- (2,(methoxycarbonyl)methanesulfanilides upon treatment with potassium carbonate in DMF furnish methyl 3-aryl-2,2-dioxo-2-thia-3-azabicyclo[n.1.0]alkane-1-carboxylates in yields ranging from 54 to 84 % (10 examples). The starting materials were obtained by sulfonylation of N-alkenylanilines with methyl (chlorosulfonyl)acetate and subsequent bromination. For the N-alkenylanilines (10 examples, 60-77 % yield) an

Mechanistic Investigation of the Reaction of Epoxides with Heterocumulenes Catalysed by a Bimetallic Aluminium Salen Complex

“…It is worth noting that this N ‐crotylaniline cyclized considerably more slowly than the corresponding N ‐allylaniline studied under the same conditions previously,6 but N ‐allylfurylamines might be quite sensitive to steric effects in the dienophile part of the molecule 4b . N ‐Allylamines are normally believed to be stable under acidic conditions and show good tolerance of, for instance, acid‐mediated reduction of nitro groups,15 hydrolysis of amides,16 and deformylations,17 but loss of allylic moieties from N ‐allylnaphthylamines was reported as a side reaction when aza‐Claisen rearrangements at elevated temperatures were attempted 18. However, if the microwave‐mediated cyclization of compound 2b was carried out in the presence of a small amount of pure water (Entry 6) or in dry MeCN (Entry 7), deallylation was prevented and good conversion to the dehydrophenanthrine 6b was achieved.…”

Two Distinct Conformations of GABA Locked by Embedding in the Bicyclo[3.1.0]hexane Core Structure

“…[1][2][3][4][5][6][7][8][9][10][11][12] They have been used as conformationally locked analogues of nucleoside building blocks [9][10][11][12] and as intrinsically interesting building blocks in numerous other applications. [13][14][15][16] They have been reported as intermediates in natural compound synthesis, [17] or as constituents of bioactive compounds, [18,19] novel materials, [20] and catalysts. [21] Methanoproline 1, a naturally occurring inhibitor of proline metabolism, [1] and 3-azabicyclo[3.1.0]hex-6-ylamine 2, a constituent of the potent broad-spectrum antibiotic trovafloxacin, [2] are particularly prominent examples.…”

Access to a Wide Range of Sultams by Cyclodialkylation of α‐Substituted Methanesulfonanilides

“…[9] Indeed, upon treatment with CAN in acetonitrile/water at 0°C, the monocyclic sultams 19d and 20d as well as the bicyclic ones 34d, 35d, 36d, and 37d gave the nitrogen-deprotected sultams 45 and 46 as well as 47-50, respectively, within 1-2 h in yields ranging from 67-84 % (see Scheme 9, Table 6). [9] Indeed, upon treatment with CAN in acetonitrile/water at 0°C, the monocyclic sultams 19d and 20d as well as the bicyclic ones 34d, 35d, 36d, and 37d gave the nitrogen-deprotected sultams 45 and 46 as well as 47-50, respectively, within 1-2 h in yields ranging from 67-84 % (see Scheme 9, Table 6).…”

“…Subsequently, a simpler and more efficient protocol for the cyclodialkylation process was completed within 30 min in the presence of a strong base such as dimsylsodium [generated by adding sodium hydride to dimethyl sulf-Scheme 5. An initial attempt to prepare 26a according to a previously published procedure [9] gave at best low yields or none of the desired product (see Scheme 6). For details, see Table 3.…”

“…[9] Scheme 1. Upon treatment with K 2 CO 3 in N,N-dimethylformamide (DMF) or NaH in dimethyl sulfoxide [a] 5028 (DMSO), N-(2,3-dibromopropyl)-α-toluenesulfonanilides furnished different 1,3-diaryl-2-thia-3-azabicyclo[3.1.0]hexane 2,2-dioxides in good to excellent yields (51-88 %, 16 examples).…”