The Synthetic Potential of the Isocyanide‐Cyanide Rearrangement

Abstract

Excellent chemical and optical yields (>96% retention) of cyanides are achieved by vapor phase thermolysis or short contact flow thermolysis of isocyanides. trans-2-Butenyl isocyanide rearranges without concomitant allylic isomerization to trans-2-butenyl cyanide. Optically active 1 -(formyloxymethyl)-2-phenylethyl cyanide is obtained from optically active L-phenylalanine as a new type of chiral pool synthon.

Practical Synthesis of Optically Active α,α-Disubstituted Malonamic Acids through Asymmetric Hydrolysis of Malonamide Derivatives with Rhodococcus sp. CGMCC 0497

“…( R )-2-Cyano-2-methyl-3-phenylpropionic Acid Ethyl Ester 8. To a solution of ( R )-2-benzyl-2-methylmalonamic acid 5a (33 mg, 0.16 mmol) in dry DMF (0.3 mL) were added ethyl bromide (0.32 mmol), and solid K 2 CO 3 (0.32 mmol) at room temperature. After 24 h, the resulting mixture was poured into water, extracted with ether, washed, and dried on Na 2 SO 4 .…”

Isonitrile–nitrile rearrangement promoted by samarium(ii) iodide

“…(1)]. [1][2][3] This implies that the bond-forming and -breaking steps occur simultaneously and that there is little development of charge in the transition state. This rearrangement occurs at high temperature (250-280 °C) and is believed to take place via a radical intermediate.…”

“…8 During the course of investigations on reactions promoted by samarium(ii) iodide we had an opportunity to study the reaction of penicillanate 1 in the presence of this powerful single electron-transferring agent [eqn. (2)].…”