New Uses for the Burgess Reagent in Chemical Synthesis: Methods for the Facile and Stereoselective Formation of Sulfamidates, Glycosylamines, and Sulfamides

Abstract

Although the Burgess reagent (methoxycarbonylsulfamoyltriethylammonium hydroxide, inner salt) has found significant use in chemical synthesis as a dehydrating agent, almost no work has been directed towards its potential in other synthetic applications. As this article will detail, we have found that the Burgess reagent is remarkably effective at accomplishing a number of non-dehydrative synthetic tasks when applied to appropriate substrates, such as the formation of sulfamidates from 1,2-diols or epoxyalcohols, alpha- and beta-glycosylamines from carbohydrates, and cyclic sulfamides from 1,2-aminoalcohols. Beyond delineating the power of these new reaction manifolds, we also describe the construction of a group of alternative Burgess-type reagents that extends the scope of these new reactions even further.

The Synthesis of Alkyl and (Hetero)aryl Sulfonamides From Sulfamoyl Inner Salts

“…Gratifyingly, however, phenylmagnesium bromide added cleanly to commercial inner salt 1 ( Table 1, entry 1), yielding the desired benzyl (phenylsulfonyl)carbamate in 56% yield after chromatography. Similar reactivity was observed with readily prepared inner salts 2 32 and 3 28 (Table 1, entries 2-3). 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 General conditions: 0 °C, 0.15 M final concentration, 60-90 min.…”

Copper-(s)-N-methylpyrrolidine-2-carboxylate catalyzed N-Arylation of N⁵h-1,2,5-thiadiazolidine 1,1-dioxides

“…R f =0.29 [18] Compound 2c was prepared using 1b and was obtained as a white solid in 53% yield using [18] Compound 2e was prepared using 1b and was obtained as a white solid in 19% yield. …”

“…Starting N 2 -substituted, N 5 H -1,2,5-thiadiazolidines were prepared from the chlorosulfonyl isocyanate (CSI) according to established synthetic procedures [12][13][14][15][18][19][20].…”

New Options for the Reactivity of the Burgess Reagent with Epoxides in Both Racemic and Chiral Auxiliary Modes – Structural and Mechanistic Revisions, Computational Studies, and Application to Synthesis

“…The investigations described in this paper have led to considerable revisions of some previously reported structures as well as adjustments in the current mechanism of the reaction of the Burgess reagent with epoxides and diols. [22] One of the reasons for the erroneous structural assignments may be the fact that almost all reactions performed to date on diols and epoxides were carried out on conformationally flexible substrates (exceptions being cyclohexene oxide, some of the 2,3-hydroxyoxiranes, [14] and carbohydrates [11] ). The reactivity manifolds as well as identification of products and stereochemical assignments are different in cyclic oxiranes, diols, and amino alcohols.…”

“…(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) closures feature the preparation of α-and β-glycosylamines from carbohydrates, [11] sulfamidates from 1,2-diols, [12] disulfides from thiols, [13] sulfamidates from 2,3-epoxy alcohols, [14] sulfamides from amino alcohols, [15] and fiveand seven-membered sulfamidates from epoxides. [16] The reactivity of epoxides with the Burgess reagent is especially noteworthy because they were believed to be inert to the action of this reagent as recently as a decade ago.…”