[3,3]-Sigmatropic rearrangements represent powerful methods in the toolbox of synthetic organic chemists for the stereoselective construction of carbon-carbon as well as carbon-heteroatom bonds. Thus, the allyl cyanate/isocyanate rearrangement, although still underused for the preparation of allylamine derivatives, offers clear advantages over other similar methods. It usually occurs at or below ambient temperature with no need to use any metal catalyst, in a stereospecific way, and with a complete transfer of chirality. Moreover, combined with the high reactivity of the resulting isocyanates towards nucleophiles, this rearrangement gives access to various classes of compounds with wide structural and functional diversity. This microreview provides an overview of synthetic applications of this rearrangement since its discovery, with particular emphasis on its utility for the synthesis of complex nitrogen‐containing molecules such as natural products.
Ichikawa rearrangement: a tool for preparation of allylamines, amino acid derivatives and aza-heterocycles
Total synthesis of lacosamide.
Stecko, S., J. Org. Chem. 2014, 79, 6342-6346;

Synthesis of β- and γ-hydroxy α-amino acids via enzymatic kinetic resolution and cyanate-to-isocyanate rearrangement.
Szcześniak, P.; Październiok-Holewa, A.; Klimczak, U.; Stecko, S., J. Org. Chem. 2014, 79, 11700-11713;

An approach to asymmetric synthesis of β-aryl alanines by Pd(0)-catalyzed cross-coupling and cyanate-to-isocyanate rearrangement.
Szcześniak, P.; Stecko, S., RSC Adv. 2015, 5, 30882-30888;

The synthesis of 5-amino-dihydrobenzo[b]oxepines and 5-amino-dihydrobenzo[b]azepines via Ichikawa rearrangement and ring-closing metathesis.
Chwastek, M.; Pieczykolan, M.; Stecko, S., J. Org. Chem. 2016, 81, 9046-9074;

The synthesis of α,α-disubstituted α-amino acids via Ichikawa rearrangement.
Szcześniak, P.; Pieczykolan, M.; Stecko, S., J. Org. Chem. 2016, 81, 1057-1074;

The synthesis of chiral β,β-diaryl allylic alcohols and their use in the preparation of α-tertiary allylamines and quaternary α-amino acids.
Pieczykolan, M.; Narczyk, A.; Stecko, S., J. Org. Chem. 2017, 82, 5636-5651;

The synthesis of non-racemic β-alkyl-β-aryl-disubstituted allyl alcohols and their transformation into allylamines and amino acids bearing a quaternary stereocenter.
Narczyk, A.; Pieczykolan, M.; Stecko, S., Org. Biomol. Chem. 2018, 16, 3921-3946
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