86
3 The Reactivity of Nitrile Imines
typically generates the corresponding aniline. This degradation pathway has been
shown to be active in a number of NI species [227, 243, 245, 246].
References
1. Huisgen R, Seidel M, Wallbillich G, Knupfer H (1962) Diphenyl-nitrilimin und seine 1.3dipolaren additionen an alkene und alkine. Tetrahedron 17:3–29
2. Clovis JS, Eckell A, Huisgen R, Sustmann R, Wallbillich G, Weberndörfer V (1967) 1.3Dipolare Cycloadditionen, XXVIII. Diphenylnitrilimin und arylkonjugierte Alkene. Chem
Ber 100:1593–1601
3. Huisgen R, Sustmann R, Wallbillich G (1967) 1.3-Dipolare Cycloadditionen, XXIX.
Orientierungsphänomene bei der Anlagerung von Nitriliminen an α.β-ungesättigte
Carbonester, Vinyläther und Enamine. Chem Ber 100:1786–1801
4. Huisgen R, Knupfer H, Sustmann R, Wallbillich G, Weberndörfer V (1967) 1.3-Dipolare
Cycloadditionen, XXVII. Zur Anlagerung des Diphenylnitrilimins an nichtkonjugierte Alkene
und Alkine; Sterischer Ablauf, Orientierung un Substituenteneinfluß. Chem Ber 100:1580–
1592
5. Strauss A, Otto H-H (1997) 1,3-Cycloadditions to highly substituted, strained double
bonds: Spiro β-lactams From α-methylidene-β-lactams by reactions with diphenylnitrilimine,
acetonitrile oxide, nitrones, and diazomethane. Helv Chim Acta 80:1823–1830
6. Sustmann R (1971) A simple model for substituent effects in cycloaddition reactions. I.
1,3-dipolar cycloadditions. Tetrahedron Lett 12:2717–2720
7. Houk KN, Sims J, Watts CR, Luskus LJ (1973) Origin of reactivity, regioselectivity, and
periselectivity in 1,3-dipolar cycloadditions. J Am Chem Soc 95:7301–7315
8. Houk KN, Sims J, Duke RE, Strozier RW, George JK (1973) Frontier molecular orbitals of
1,3 dipoles and dipolarophiles. J Am Chem Soc 95:7287–7301
9. Houk KN (1975) Frontier molecular orbital theory of cycloaddition reactions. Acc Chem Res
8:361–369
10. Chandra AK, Tho Nguyen M (1998) Approach to regiochemistry using local softness in
1,3-Dipolar cycloadditions. J Comput Chem 19:195–202
11. Molteni G, Ponti A (2017) The nitrilimine-alkene cycloaddition regioselectivity rationalized
by density functional theory reactivity indices. Molecules 22:202
12. Ponti A, Molteni G (2001) DFT-based quantitative prediction of regioselectivity:
cycloaddition of nitrilimines to methyl propiolate. J Org Chem 66:5252–5255
13. Ríos-Gutiérrez M, Domingo LR (2019) The carbenoid-type reactivity of simplest nitrile imine
from a molecular electron density theory perspective. Tetrahedron 75:1961–1967
14. Shimizu T, Hayashi Y, Nishio T, Teramura K (1984) The reaction of N-Aryl-Cethoxycarbonylnitrilimine with olefins. Bull Chem Soc Jpn 57:787–790
15. Chiericato M, Dalla Croce P, Carganico G, Maiorana S (1979) 1,3-dipolar cycloadditions.
reactions of nitrile imines with 1,2-disubstituted alkenes. J Heterocycl Chem 16:383–384
16. Green B, Sheu K (1994) Synthesis of steroidal D-ring fused pyrazolines: study of
regiochemistry of addition. Steroids 59:479–484
17. Chandanshive JZ, González PB, Tiznado W, Bonini BF, Caballero J, Femoni C, Comes
Franchini M (2012) 1,3-dipolar cycloaddition of nitrile imines with α, β-unsaturated lactones,
thiolactones and lactams: synthesis of ring-fused pyrazoles. Tetrahedron 68:3319–3328
18. Molteni G, Ponti A (2003) Assessment of mechanistic hypotheses of 1,3-dipolar cycloaddition
of (Arylsulfonyl)allene to nitrilimines by DFT reactivity indices. Tetrahedron 59:5225–5229
19. Emamiam S (2015) Understanding the molecular mechanism and regioselectivity in the
synthesis of celecoxib via a domino reaction: a DFT study. J Mol Graph Model 60:155–161
20. Bonini B, Franchini M, Gentili D, Locatelli E, Ricci A (2009) 1,3-dipolar cycloaddition of
nitrile imines with functionalized acetylenes: regiocontrolled Sc(OTf) 3 -catalyzed synthesis
of 4- and 5-substituted pyrazoles. Synlett 2009:2328–2332
3 The Reactivity of Nitrile Imines
typically generates the corresponding aniline. This degradation pathway has been
shown to be active in a number of NI species [227, 243, 245, 246].
References
1. Huisgen R, Seidel M, Wallbillich G, Knupfer H (1962) Diphenyl-nitrilimin und seine 1.3dipolaren additionen an alkene und alkine. Tetrahedron 17:3–29
2. Clovis JS, Eckell A, Huisgen R, Sustmann R, Wallbillich G, Weberndörfer V (1967) 1.3Dipolare Cycloadditionen, XXVIII. Diphenylnitrilimin und arylkonjugierte Alkene. Chem
Ber 100:1593–1601
3. Huisgen R, Sustmann R, Wallbillich G (1967) 1.3-Dipolare Cycloadditionen, XXIX.
Orientierungsphänomene bei der Anlagerung von Nitriliminen an α.β-ungesättigte
Carbonester, Vinyläther und Enamine. Chem Ber 100:1786–1801
4. Huisgen R, Knupfer H, Sustmann R, Wallbillich G, Weberndörfer V (1967) 1.3-Dipolare
Cycloadditionen, XXVII. Zur Anlagerung des Diphenylnitrilimins an nichtkonjugierte Alkene
und Alkine; Sterischer Ablauf, Orientierung un Substituenteneinfluß. Chem Ber 100:1580–
1592
5. Strauss A, Otto H-H (1997) 1,3-Cycloadditions to highly substituted, strained double
bonds: Spiro β-lactams From α-methylidene-β-lactams by reactions with diphenylnitrilimine,
acetonitrile oxide, nitrones, and diazomethane. Helv Chim Acta 80:1823–1830
6. Sustmann R (1971) A simple model for substituent effects in cycloaddition reactions. I.
1,3-dipolar cycloadditions. Tetrahedron Lett 12:2717–2720
7. Houk KN, Sims J, Watts CR, Luskus LJ (1973) Origin of reactivity, regioselectivity, and
periselectivity in 1,3-dipolar cycloadditions. J Am Chem Soc 95:7301–7315
8. Houk KN, Sims J, Duke RE, Strozier RW, George JK (1973) Frontier molecular orbitals of
1,3 dipoles and dipolarophiles. J Am Chem Soc 95:7287–7301
9. Houk KN (1975) Frontier molecular orbital theory of cycloaddition reactions. Acc Chem Res
8:361–369
10. Chandra AK, Tho Nguyen M (1998) Approach to regiochemistry using local softness in
1,3-Dipolar cycloadditions. J Comput Chem 19:195–202
11. Molteni G, Ponti A (2017) The nitrilimine-alkene cycloaddition regioselectivity rationalized
by density functional theory reactivity indices. Molecules 22:202
12. Ponti A, Molteni G (2001) DFT-based quantitative prediction of regioselectivity:
cycloaddition of nitrilimines to methyl propiolate. J Org Chem 66:5252–5255
13. Ríos-Gutiérrez M, Domingo LR (2019) The carbenoid-type reactivity of simplest nitrile imine
from a molecular electron density theory perspective. Tetrahedron 75:1961–1967
14. Shimizu T, Hayashi Y, Nishio T, Teramura K (1984) The reaction of N-Aryl-Cethoxycarbonylnitrilimine with olefins. Bull Chem Soc Jpn 57:787–790
15. Chiericato M, Dalla Croce P, Carganico G, Maiorana S (1979) 1,3-dipolar cycloadditions.
reactions of nitrile imines with 1,2-disubstituted alkenes. J Heterocycl Chem 16:383–384
16. Green B, Sheu K (1994) Synthesis of steroidal D-ring fused pyrazolines: study of
regiochemistry of addition. Steroids 59:479–484
17. Chandanshive JZ, González PB, Tiznado W, Bonini BF, Caballero J, Femoni C, Comes
Franchini M (2012) 1,3-dipolar cycloaddition of nitrile imines with α, β-unsaturated lactones,
thiolactones and lactams: synthesis of ring-fused pyrazoles. Tetrahedron 68:3319–3328
18. Molteni G, Ponti A (2003) Assessment of mechanistic hypotheses of 1,3-dipolar cycloaddition
of (Arylsulfonyl)allene to nitrilimines by DFT reactivity indices. Tetrahedron 59:5225–5229
19. Emamiam S (2015) Understanding the molecular mechanism and regioselectivity in the
synthesis of celecoxib via a domino reaction: a DFT study. J Mol Graph Model 60:155–161
20. Bonini B, Franchini M, Gentili D, Locatelli E, Ricci A (2009) 1,3-dipolar cycloaddition of
nitrile imines with functionalized acetylenes: regiocontrolled Sc(OTf) 3 -catalyzed synthesis
of 4- and 5-substituted pyrazoles. Synlett 2009:2328–2332