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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-213-00165
C-1 Building Blocks in Organic Synthesis 2

2.5.5 Reaction of Formaldehyde with Organometallic Reagents

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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

Formaldehyde is one of the most important single-carbon electrophiles; it is inexpensive and can be used in many organic reactions and thus in natural product synthesis. However, there are scant examples of the application of formaldehyde with organometallic reagents in synthesis. This may be due to the properties of formaldehyde. Monomeric formaldehyde tends to polymerize rapidly to give poorly reactive species such as paraformaldehyde and the trimer trioxane. Paraformaldehyde and trioxane are depolymerized thermally; however, thermal cracking produces highly toxic, gaseous formaldehyde that rapidly repolymerizes. Alternatively, paraformaldehyde and trioxane can be depolymerized with Lewis acids, but this introduces new factors, such as corrosion, toxic waste disposal, and difficult handling. Formaldehyde is also available as an aqueous solution, known as formalin, but this approach is often unsuitable due to the instability of the organometallic compounds in the presence of water. This section discusses all that can be achieved despite these factors.

Key words

formaldehyde - hydroxymethylation - aldol reaction - Prins reaction - carbonyl-ene reaction - hydroformylation - hydrohydroxymethylation
 
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