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. 2021 Aug 3;57(62):7610-7624.
doi: 10.1039/d1cc02836g.

Recent advances in palladium-catalyzed (hetero)annulation of C[double bond, length as m-dash]C bonds with ambiphilic organo(pseudo)halides

Hui-Qi Ni  1 , Phillippa Cooper  1 , Keary M Engle  1
Affiliations

Recent advances in palladium-catalyzed (hetero)annulation of C[double bond, length as m-dash]C bonds with ambiphilic organo(pseudo)halides

Hui-Qi Ni et al. Chem Commun (Camb). .

Abstract

Palladium has proven to be effective in catalyzing the (hetero)annulation of C[double bond, length as m-dash]C bonds with ambiphilic organo(pseudo)halides. Through the employment of appropriate ambiphilic coupling partners, efficient annulation of a variety of allenes, 1,3-dienes, strained alkenes, styrenes, and other C[double bond, length as m-dash]C bond variants can be achieved to provide direct access to numerous useful hetero- and carbocyclic scaffolds. In this Feature Article, we summarize palladium-catalyzed (hetero)annulation methods reported since 2005 (spanning just over 15 years) and discuss outstanding challenges in this area of study.

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Figures

Figure 1:
Figure 1:
Representative C=C bond starting materials and heterocycle products.
Figure 2:
Figure 2:
Pd(0)-catalyzed [3+2] synthesis of pterocarpan derivatives.
Scheme 1:
Scheme 1:
The mechanism for Pd(0)-catalyzed heteroannulation of allenes.
Scheme 2:
Scheme 2:
Pd(0)-catalyzed reactions of allenylphosphonates and related allenes.
Scheme 3:
Scheme 3:
Highly regioselective Pd(0)-catalyzed annulation of allenes bearing heteroatom substituents.
Scheme 4:
Scheme 4:
Annulation of diarylvinylidenecyclopropanes.
Scheme 5:
Scheme 5:
Phosphine-free Pd(0)-catalyzed heteroannulation of 2-alkyl-1,2-dienols.
Scheme 6:
Scheme 6:
Enantioselective annulation of allenes with 2-iodoanilines.
Scheme 7:
Scheme 7:
Pd(0)/PC-Phos-catalyzed enantioselective inter- molecular denitrogenative of benzotriazoles and annulation of allenes.
Scheme 8:
Scheme 8:
Pd(0)-catalyzed intermolecular [4+2] annulation of allenamides with (Z)-3-iodo allylic nucleophiles.
Scheme 9:
Scheme 9:
The mechanism for Pd(0)-catalyzed heteroannulation of 1,3-dienes.
Scheme 10:
Scheme 10:
Pd(0)-catalyzed annulation of 1,3-dienes with 2-iodoaryl acetates.
Scheme 11:
Scheme 11:
Pd(0)-catalyzed heteroannulation of functional 1-alkoxy-1,3-butadienes with 2-iodophenols and 2-iodoanilines.
Scheme 12:
Scheme 12:
Pd(0)-catalyzed enantioselective heteroannulation of 1,3-dienes.
Scheme 13:
Scheme 13:
Pd(0)-catalyzed denitrogenative annulation of 1,3-dienes via a Dimroth-type equilibrium.
Scheme 14:
Scheme 14:
Pd(0)-catalyzed heteroannulation of 1,3-diene synthons.
Scheme 15:
Scheme 15:
Pd(0)-catalyzed ring expansion/annulation cascade of cyclobutanes.
Scheme 16:
Scheme 16:
Pd(0)-catalyzed annulation of strained alkenes with aryl heterocycles.
Scheme 17:
Scheme 17:
Pd(0)-catalyzed annulation of norbornadiene with haloanilines and halobenzamides.
Scheme 18:
Scheme 18:
Pd(0)-catalyzed tandem decarboxylative/ amination/Heck-type/annulation reaction.
Scheme 19:
Scheme 19:
Pd(0)-catalyzed enantioselective annulation of NBE/NBD.
Scheme 20:
Scheme 20:
Pd(0)-catalyzed C–H annulation of NBE/NBD with 5-membered heteroaryl halides.
Scheme 21:
Scheme 21:
Pd(0)-catalyzed annulation of azabicyclic olefins with 2-iodophenol/anilines.
Scheme 22:
Scheme 22:
Pd(0)-catalyzed annulation of azabicyclic olefins with 2-iodophenols and -anilines under microwave irradiation.
Scheme 23:
Scheme 23:
Pd(0)/LA-mediated domino reaction of pentafulvene derived diazabicyclic olefins.
Scheme 24:
Scheme 24:
(A) Introduction of pterocarpan; (B) Pd(II)-mediated Heck-1,2-oxyarylation.
Scheme 25:
Scheme 25:
Costa and Eberlin’s reported mechanism for Pd(0)-catalyzed heteroannulation of styrenes.
Scheme 26:
Scheme 26:
Pd(0)-catalyzed one-pot synthesis of trans-dihydrobenzofurans from 2-aminophenols.
Scheme 27:
Scheme 27:
Pd(0)-catalyzed enantioselective synthesis of dihydrobenzofurans.
Scheme 28:
Scheme 28:
Pd(0)-catalyzed annulation of C60 with a variety of 2-iodoanilines.
Scheme 29:
Scheme 29:
Pd(0)-catalyzed intermolecular carbohetero-functionalization of 2,3-dihydrofurans.
Scheme 30:
Scheme 30:
The mechanism of Pd(0)-catalyzed carboetherification and carboamination of 2,3-dihydrofurans.
Scheme 31:
Scheme 31:
Pd(0)-catalyzed γ-arylation of β, γ-unsaturated ketones.
Scheme 32:
Scheme 32:
Pd(0)-catalyzed intramolecular aminoalkylation to access polycyclic lactams.
Scheme 33:
Scheme 33:
Pd(II)-catalyzed anti-selective [3+2] annulation of non-conjugated alkenes.
Scheme 34:
Scheme 34:
The mechanism of anti-selective Pd(II)-catalyzed [3+2] annulation of non-conjugated alkenes.
Scheme 35:
Scheme 35:
Selective examples of C-H activation-based coupling partners
Scheme 36:
Scheme 36:
Other existing methodologies involving ambiphilic molecules and alkenes.
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