DalPhos Ligands

Professor Mark Stradiotto and coworkers at Dalhousie University have developed air-stable Dalphos, which contains the bulky di(1-adamantyl)phosphino [P(1-Ad)₂] fragment. These chelating N,P ligands are useful for previously unprecedented Pd-catalyzed C-N and C-C bond formation. Both Me-DalPhos (Cat. No. 751413) and Mor-DalPhos (Cat. No. 751618) allow for Pd-catalyzed ammonia cross-coupling. In particular, the more reactive Mor-Dalphos improved the scope and utility of ammonia coupling at room temperature.

Cat. No. 759198

Cat. No. 751618

Cat. No. 751413

Benefits of DalPhos Ligands:

• Monoarylation of ammonia, hydrazine and acetone
• Air-stable
• Good functional group tolerance
• Mild conditions

Me-DalPhos featuring an ortho-dimethylamino group has been shown to be a valuable ligand for the Pd-catalyzed cross-coupling of aryl chlorides and amines (including ammonia). The highly efficient Mor-Dalphos, where the dimethylamino group is replaced by morpholine, easily enables the ammonia coupling of a range of aryl chlorides and aryl tosylates.

Cross-Coupling of Ammonia

Mor-DalPhos can be used for the first Pd-catalyzed cross-coupling of aryl chlorides and tosylates with hydrazine. The Stradiotto group also explored the scope of the reaction of aryl hydrazines with benzaldehydes to afford the corresponding aryl hydrazones.

Cross-Coupling of Hydrazine

The direct arylation of acetone with a range of aryl halides and tosylates has been reported with good monoarylation selectivity. The use of Mor-DalPhos has a key impact on the rate and selectivity of this reaction.

Cross-Coupling of Acetone

The use of Mor-DalPhos for the gold-catalyzed hydroamination of internal aryl alkynes with dialkylamines has been studied. This gold precatalyst featuring a P,N-ligand effects the stereoselective addition of a variety of functionalized dialkylamines to unsymmetrical internal arylacetylenes.

Gold-Catalyzed Hydroamination

References

1. Lundgren R, Peters B, Alsabeh P, Stradiotto M. 2010. A P,N-Ligand for Palladium-Catalyzed Ammonia Arylation: Coupling of Deactivated Aryl Chlorides, Chemoselective Arylations, and Room Temperature Reactions. Angewandte Chemie International Edition. 49(24):4071-4074. https://doi.org/10.1002/anie.201000526

2. Lundgren RJ, Stradiotto M. 2010. Transition-Metal-Catalyzed Trifluoromethylation of Aryl Halides. Angew. Chem. Int. Ed.. 49(49):9322-9324. https://doi.org/10.1002/anie.201004051

3. Hesp KD, Lundgren RJ, Stradiotto M. 2011. Palladium-Catalyzed Mono-?-arylation of Acetone with Aryl Halides and Tosylates. J. Am. Chem. Soc.. 133(14):5194-5197. https://doi.org/10.1021/ja200009c

4. Lundgren R, Sappong-Kumankumah A, Stradiotto M. 2010. A Highly Versatile Catalyst System for the Cross-Coupling of Aryl Chlorides and Amines. Chem. Eur. J.. 16(6):1983-1991. https://doi.org/10.1002/chem.200902316

5. Hesp KD, Stradiotto M. 2010. Stereo- and Regioselective Gold-Catalyzed Hydroamination of Internal Alkynes with Dialkylamines. J. Am. Chem. Soc.. 132(51):18026-18029. https://doi.org/10.1021/ja109192w