Chapter 3
The Reactivity of Nitrile Imines
Abstract One of the most unique properties of nitrile imines in comparison to other
1,3-dipoles is their diverse reactivity profile with a number of distinct substrates.
This chapter aims to categorise the different transformations of the dipole that
have been reported in the literature over the past 60 years. Of particular utility
is the conventional 1,3-dipolar cycloaddition reaction between the nitrile imine
and unsaturated carbon-carbon bonds. While further research is required to fully
comprehend the factors determining the rate and regioselectivity of such reactions,
these aspects are also discussed. Nitrile imines also exhibit substantial reactivity with
a number of nucleophiles, particularly softer examples such as carboxylic acids and
thiols. In the absence of any reaction partners, certain species of nitrile imine are also
labile to undergo intramolecular rearrangement, dimerisation, or decomposition.
Keywords Nitrile imine · 1,3-dipole · Reactivity · 1,3-dipolar cycloaddition ·
Carboxylic acids · Nucleophiles · Rearrangements
NIs exhibit a broad scope of reactivity with a number of different substrates. The
inherent property of 1,3-dipoles to undergo 1,3-dipolar cycloaddition with olefins
and alkynes is shared by NIs, but reactions with various nucleophiles are also well
documented.
3.1 1,3-Dipolar Cycloaddition
The cycloaddition of a 1,3-dipole with an appropriate dipolarophile, typically
a carbon-carbon or carbon-heteroatom double or triple bond, is a powerful
reaction manifold that is broadly applicable in organic synthesis. NIs have been
widely characterised to undergo this type of reaction with a number of different
dipolarophiles.
© Springer Nature Switzerland AG 2020
C. Jamieson and K. Livingstone, The Nitrile Imine 1,3-Dipole,
https://doi.org/10.1007/978-3-030-43481-6_3
37
The Reactivity of Nitrile Imines
Abstract One of the most unique properties of nitrile imines in comparison to other
1,3-dipoles is their diverse reactivity profile with a number of distinct substrates.
This chapter aims to categorise the different transformations of the dipole that
have been reported in the literature over the past 60 years. Of particular utility
is the conventional 1,3-dipolar cycloaddition reaction between the nitrile imine
and unsaturated carbon-carbon bonds. While further research is required to fully
comprehend the factors determining the rate and regioselectivity of such reactions,
these aspects are also discussed. Nitrile imines also exhibit substantial reactivity with
a number of nucleophiles, particularly softer examples such as carboxylic acids and
thiols. In the absence of any reaction partners, certain species of nitrile imine are also
labile to undergo intramolecular rearrangement, dimerisation, or decomposition.
Keywords Nitrile imine · 1,3-dipole · Reactivity · 1,3-dipolar cycloaddition ·
Carboxylic acids · Nucleophiles · Rearrangements
NIs exhibit a broad scope of reactivity with a number of different substrates. The
inherent property of 1,3-dipoles to undergo 1,3-dipolar cycloaddition with olefins
and alkynes is shared by NIs, but reactions with various nucleophiles are also well
documented.
3.1 1,3-Dipolar Cycloaddition
The cycloaddition of a 1,3-dipole with an appropriate dipolarophile, typically
a carbon-carbon or carbon-heteroatom double or triple bond, is a powerful
reaction manifold that is broadly applicable in organic synthesis. NIs have been
widely characterised to undergo this type of reaction with a number of different
dipolarophiles.
© Springer Nature Switzerland AG 2020
C. Jamieson and K. Livingstone, The Nitrile Imine 1,3-Dipole,
https://doi.org/10.1007/978-3-030-43481-6_3
37