Abstract: | N‐sulfinylacylamides R‐C(=O)‐N=S=O react with (CF3)2BNMe2 ( 1 ) to form, by 2+4] cycloaddition, six‐membered rings cyclo‐(CF3)2B‐NMe2‐S(=O)‐N=C(R)‐O for R = Me ( 2 ), t‐Bu ( 3 ), C6H5 ( 4 ), and p‐CH3C6H4 ( 5 ) while N‐sulfinylcarbamic acid esters R‐O‐C(=O)‐N=S=O react with 1 to yield mixtures of six‐membered (cyclo‐(CF3)2B‐NMe2‐S(=O)‐N=C(OR)‐O) and four‐membered rings (cyclo‐(CF3)2B‐NMe2‐S(=O)‐N(C=O)OR) for R = Me ( 6 and 9 ), Et ( 7 and 10 ), and C6H5 ( 8 and 11 ). The structure of 5 has been determined by X‐ray diffraction. |