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van Leeuwen, P. W. N. M.: 2014 Science of Synthesis, 2013/8: C-1 Building Blocks in Organic Synthesis 2 DOI: 10.1055/sos-SD-213-00137
C-1 Building Blocks in Organic Synthesis 2

2.5.2 Cyanation of Epoxides

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Book

Editor: van Leeuwen, P. W. N. M.

Authors: Ballini, R.; Belderrain, T. R.; Bruneau, C.; Cokoja, M.; Dong, D.; Fischmeister, C.; Grushin, V. V.; Hu, J.; Ibrahim, H.; Iwasawa, N.; Kaposi, M.; Kühn, F. E.; Lishchynskyi, A.; Merino, P.; Molander, G. A.; Müller, C.; MuÇoz-Molina, J. M.; Neumann, H.; Ni, C.; Nicasio, M. C.; Novák, P.; Nozaki, K.; Ouali, A.; Petrini, M.; Rutjes, F. P. J. T.; Ryu, D.; Schoonen, L.; Schranck, J.; Taillefer, M.; Takahashi, K.; Takaya, J.; te Grotenhuis, C.; Witt, J.; Zhang, N.

Title: C-1 Building Blocks in Organic Synthesis 2

Subtitle: Alkenations, Cross Couplings, Insertions, Substitutions, and Halomethylations

Print ISBN: 9783131751218; Online ISBN: 9783132064515; Book DOI: 10.1055/b-003-125817

1st edition © 2014. Thieme. All rights reserved.
Georg Thieme Verlag KG, Stuttgart

Subjects: C-1 Building Blocks in Organic Synthesis

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Parent publication

Title: Science of Synthesis

DOI: 10.1055/b-00000101

Type: Multivolume Edition

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Abstract

Opening of epoxides with cyanide yields β-cyanohydrins (β-hydroxy nitriles), which are synthetically versatile intermediates that can be readily converted into a wide array of new functional groups. During the ring-opening reaction two contiguous stereocenters are generated, which can be controlled in several ways. When the reaction is performed without activation, terminal epoxides can be opened such that attack will take place at the least hindered carbon atom. Addition of a hard Lewis acidic catalyst will lead to activation of the epoxide, due to coordination to the epoxide oxygen atom, allowing the use of electronically and sterically more demanding substrates. Furthermore, ligands surrounding the metal of the catalyst can direct to which position of the epoxide attack will take place. If enantiopure ligands are used, meso-epoxides can be desymmetrized, resulting in the formation of a single enantiomer of the β-hydroxy nitrile product.

Key words

epoxide - cyanide - cyanation - nucleophilic ring opening - Lewis acid activation - β-hydroxy nitrile - β-cyanohydrin
 
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