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The cyanation of aldimines, generated in situ from N-benzyloxycarbonylamino- and N-tosylamino-benzyl phenylsulfones, to the corresponding N-protected α-aminobenzyl nitriles has been achieved by eco-friendly Strecker reactions using potassium hexacyanoferrate(II) as a cyanide source, benzoyl chloride as a promoter, and potassium hydroxide as a base. The protocol has the advantages of using a nontoxic, nonvolatile and inexpensive cyanating agent, employing a simple work-up procedure and producing high yields. [ABSTRACT FROM AUTHOR]

Abstract: We herein report a robust catalyst‐free cross‐coupling between ArI(OAc)2 and α‐stannyl nitriles, aided by TMSOTf. The transformation introduces a cyanoalkyl group to the ortho position of ArI(OAc)2 and simultaneously reduces the aryl iodine(III) to iodide, thus providing α‐(2‐iodoaryl) nitrile as the product. This transformation could be completed within 5 min at −78 °C and features superb functional‐group tolerance and efficient scalability. DFT calculations indicate that the formation of a ketenimine(aryl)iodonium intermediate and subsequent [3,3]‐sigmatropic rearrangement are involved as key steps. [ABSTRACT FROM AUTHOR]

Abstract: We herein report a robust catalyst‐free cross‐coupling between ArI(OAc)2 and α‐stannyl nitriles, aided by TMSOTf. The transformation introduces a cyanoalkyl group to the ortho position of ArI(OAc)2 and simultaneously reduces the aryl iodine(III) to iodide, thus providing α‐(2‐iodoaryl) nitrile as the product. This transformation could be completed within 5 min at −78 °C and features superb functional‐group tolerance and efficient scalability. DFT calculations indicate that the formation of a ketenimine(aryl)iodonium intermediate and subsequent [3,3]‐sigmatropic rearrangement are involved as key steps. [ABSTRACT FROM AUTHOR]