Chemoselective Reactions of Functionalized Sulfonyl Halides

Abstract

Chemoselective transformations of functionalized sulfonyl fluorides and chlorides are surveyed comprehensively. It is shown that sulfonyl fluorides provide an excellent selectivity control in their reactions. Thus, numerous conditions are tolerated by the SO2F group – from amide and ester formation to directed ortho‐lithiation and transition‐metal‐catalyzed cross‐couplings. Meanwhile, sulfur (VI) fluoride exchange (SuFEx) is also compatible with numerous functional groups, thus confirming its title of “another click reaction”. On the contrary, with a few exceptions, most transformations of functionalized sulfonyl chlorides typically occur at the SO2Cl moiety.

SNAr or Sulfonylation? Chemoselective Amination of Halo(het)arene Sulfonyl Halides for Synthetic Applications and Ultralarge Compound Library Design

“…1-( 5 5,138.8,137.3,135.0,133.3,133.0,129.6,128.3 (q,J = 282 Hz),126.5,111.0,110.1,60.8,52.1,51.9,48.7,46.0,45.7,45.5,44.8,27.1,20 H,4.96;N,10.21;S,11.69. Found: C,48.51;H,5.23;N,10.34;S,11.80.…”

“…Sulfonyl halides bearing additional functional groups are especially promising for organic synthesis and early drug discovery, especially in the design of large compound libraries, provided that selective modification at both functionalities is possible. , Examples of such reagents include ethenesulfonyl fluoride ( 1 ) and its derivatives (e.g., 2 ) and sulfonyl fluorides bearing azide (e.g., 3 ), boronic acid (e.g., 4 ), sulfonyl chloride (e.g., 5 ), or Suzuki reaction-compatible hetaryl bromide (e.g., 6 ) moieties (Figure ). A possibility of selective modification for these bifunctional substrates is ensured by either the use of two mechanistically distinct transformations or dramatic difference in the reactivity of the two available centers.…”