Non-Symmetrical Bis-Azine Biaryls from Chloroazines: A Strategy Using Phosphorus Ligand-Coupling

Alternative Approach ◽

Metal Catalyzed ◽

Traditional Approaches ◽

Coupling Partner ◽

Coupling Sequence

Distinct approaches to synthesize bis-azine biaryls are in demand as these compounds have multiple applications in the chemical sciences and are challenging targets for metal-catalyzed cross-coupling reactions. Most approaches focus on developing new reagents as the formal nucleophilic coupling partner that can function in metal-catalyzed processes. We present an alternative approach using pyridine and diazine phosphines as nucleophilic partners and chloroazines where the heterobiaryl bond is formed via a tandem SNAr-phosphorus ligand-coupling sequence. The heteroaryl phosphines are prepared from chloroazines and are bench stable solids. Using this strategy, a range of bis-azine biaryls can be formed from abundant chloroazines that would be challenging using traditional approaches and a one-pot cross-electrophile coupling of two chloroazines is feasible.

Sequential decarboxylative azide–alkyne cycloaddition and dehydrogenative coupling reactions: one-pot synthesis of polycyclic fused triazoles

Beilstein Journal of Organic Chemistry ◽

10.3762/bjoc.10.321 ◽

2014 ◽

Vol 10 ◽

pp. 3031-3037 ◽

Cited By ~ 6

Author(s):

Kuppusamy Bharathimohan ◽

Thanasekaran Ponpandian ◽

A Jafar Ahamed ◽

Nattamai Bhuvanesh

Keyword(s):

Transition Metal ◽

Cross Coupling ◽

Coupling Reactions ◽

One Pot ◽

Triazole Derivatives ◽

One Pot Synthesis ◽

Dehydrogenative Coupling ◽

Transition Metal Catalyzed ◽

Herein, we describe a one-pot protocol for the synthesis of a novel series of polycyclic triazole derivatives. Transition metal-catalyzed decarboxylative CuAAC and dehydrogenative cross coupling reactions are combined in a single flask and achieved good yields of the respective triazoles (up to 97% yield). This methodology is more convenient to produce the complex polycyclic molecules in a simple way.

A Revised Modular Approach to D8-THC and Derivatives Through Late-Stage Suzuki-Miyaura Cross-Coupling Reactions

10.26434/chemrxiv.7553444.v1 ◽

2019 ◽

Author(s):

Victor Bloemendal ◽

Floris P. J. T. Rutjes ◽

Thomas J. Boltje ◽

Daan Sondag ◽

Hidde Elferink ◽

...

Keyword(s):

Biological Activity ◽

Late Stage ◽

Medicinal Chemistry ◽

Cross Coupling ◽

Modular Approach ◽

Coupling Reactions ◽

One Pot ◽

Biologically Relevant ◽

Chemistry Research

In this manuscript we describe a modular pathway to synthesize biologically relevant (–)-trans-Δ8-THC derivatives, which can be used to modulate the pharmacologically important CB1 and CB2 receptors. This pathway involves a one-pot Friedel-Crafts alkylation/cyclization protocol, followed by Suzuki-Miyaura cross-coupling reactions and gives rise to a series of new Δ8-THC derivatives. In addition, we demonstrate using extensive NMR evidence that similar halide-substituted Friedel-Crafts alkylation/cyclization products in previous articles were wrongly assigned as the para-isomers, which also has consequence for the assignment of the subsequent cross-coupled products and interpretation of their biological activity. Considering the importance of the availability of THC derivatives in medicinal chemistry research and the fact that previously synthesized compounds were wrongly assigned, we feel this research is describing a straightforward pathway into new cannabinoids.

Monodentate Trialkylphosphines: Privileged Ligands in Metal-catalyzed Crosscoupling Reactions

Current Organic Chemistry ◽

10.2174/1385272824666200211114540 ◽

2020 ◽

Vol 24 (3) ◽

pp. 231-264 ◽

Cited By ~ 3

Author(s):

Kevin H. Shaughnessy

Keyword(s):

Transition Metal ◽

Cross Coupling ◽

Coupling Reactions ◽

Aryl Bromides ◽

Wide Range ◽

Sterically Demanding ◽

Transition Metal Catalyzed ◽

Catalyzed Reactions ◽

Phosphines are widely used ligands in transition metal-catalyzed reactions. Arylphosphines, such as triphenylphosphine, were among the first phosphines to show broad utility in catalysis. Beginning in the late 1990s, sterically demanding and electronrich trialkylphosphines began to receive attention as supporting ligands. These ligands were found to be particularly effective at promoting oxidative addition in cross-coupling of aryl halides. With electron-rich, sterically demanding ligands, such as tri-tertbutylphosphine, coupling of aryl bromides could be achieved at room temperature. More importantly, the less reactive, but more broadly available, aryl chlorides became accessible substrates. Tri-tert-butylphosphine has become a privileged ligand that has found application in a wide range of late transition-metal catalyzed coupling reactions. This success has led to the use of numerous monodentate trialkylphosphines in cross-coupling reactions. This review will discuss the general properties and features of monodentate trialkylphosphines and their application in cross-coupling reactions of C–X and C–H bonds.

Synthesis of Marine Polyacetylenes Callyberynes A−C by Transition-Metal-Catalyzed Cross-Coupling Reactions to sp Centers

The Journal of Organic Chemistry ◽

10.1021/jo052609u ◽

2006 ◽

Vol 71 (7) ◽

pp. 2802-2810 ◽

Cited By ~ 32

Author(s):

Susana López ◽

Francisco Fernández-Trillo ◽

Pilar Midón ◽

Luis Castedo ◽

Carlos Saá

Keyword(s):

Transition Metal ◽

Cross Coupling ◽

Coupling Reactions ◽

Transition Metal Catalyzed ◽

Metal-Catalyzed Cross-Coupling Reactions and More. 3 Volume Set. Edited by Armin de Meijere, Stefan Bräse and Martin Oestreich.

Angewandte Chemie International Edition ◽

10.1002/anie.201408267 ◽

2014 ◽

Vol 53 (48) ◽

pp. 13001-13002 ◽

Cited By ~ 2

Author(s):

Ian J. S. Fairlamb

Keyword(s):

Cross Coupling ◽

Coupling Reactions ◽

ChemInform Abstract: One-Pot Chemoselective Synthesis of 2,4,6,8-Tetrasubstituted Quinazolines via Microwave-Assisted Consecutive Bis-SNAr/Bis-Suzuki-Miyaura Cross-Coupling Reactions.

ChemInform ◽

10.1002/chin.201450162 ◽

2014 ◽

Vol 45 (50) ◽

pp. no-no ◽

Cited By ~ 1

Author(s):

Youssef Kabri ◽

Maxime D. Crozet ◽

Sebastien Redon ◽

Patrice Vanelle

Keyword(s):

Cross Coupling ◽

Coupling Reactions ◽

One Pot ◽

Microwave Assisted ◽

Chemoselective Synthesis

Protecting group-free, selective cross-coupling of alkyltrifluoroborates with borylated aryl bromides via photoredox/nickel dual catalysis

Proceedings of the National Academy of Sciences ◽

10.1073/pnas.1509715112 ◽

2015 ◽

Vol 112 (39) ◽

pp. 12026-12029 ◽

Cited By ~ 66

Author(s):

Yohei Yamashita ◽

John C. Tellis ◽

Gary A. Molander

Keyword(s):

Small Molecules ◽

Functional Group ◽

Cross Coupling ◽

Differential Protection ◽

Coupling Reactions ◽

Protecting Group ◽

Aryl Bromides ◽

Rapid Construction ◽

Orthogonal reactivity modes offer substantial opportunities for rapid construction of complex small molecules. However, most strategies for imparting orthogonality to cross-coupling reactions rely on differential protection of reactive sites, greatly reducing both atom and step economies. Reported here is a strategy for orthogonal cross-coupling wherein a mechanistically distinct activation mode for transmetalation of sp3-hybridized organoboron reagents enables C-C bond formation in the presence of various protected and unprotected sp2-hybridized organoborons. This manifold has the potential for broad application, because orthogonality is inherent to the activation mode itself. The diversification potential of this platform is shown in the rapid elaboration of a trifunctional lynchpin through various transition metal-catalyzed processes without nonproductive deprotection or functional group manipulation steps.