N-P Bond Formation
Phosphorylation of amines, alcohols, and sulfoximines provides various phosphoramidates, phosphorus triesters and sulfoximine-derived phosphoramidates using molecular iodine as a catalyst and H2O2 as the sole oxidant under mild reaction conditions.
J. Dhineshkumar, K. R. Prabhu, Org. Lett., 2013, 15, 6062-6065.
A diaryldiselenide catalyzes a cross-dehydrogenative nucleophilic functionalization of hydrophosphoryl compounds. Phosphorus and selenium NMR studies reveal the existence of a P-Se bond intermediate, and structural analyses indicate a stereospecific reaction.
Handoko, Z. Benslimane, P. S. Arora, Org. Lett., 2020, 22, 5806-5810.
A dual copper/photoredox-catalyzed approach for the construction of the P(O)-N bond from commercially available aromatic amines and P(O)-H compounds avoids toxic or corrosive reagents and does not require prefunctionalized substrates. The reaction has a broad substrate scope and is suitable for the synthesis of phosphonamides and phosphinamides.
K.-C. Yu, H. Li, Y.-H. Tu, H. Zhao, X.-G. Hu, Org. Lett., 2022, 24, 9130-9134.
Ethyl bromoacetate mediates a facile and efficient synthesis of primary phosphinamides from Ar2P(O)-H reagents with stable and readily available ammonium carbonate as an ammonia source under mild and simple conditions, without any metal catalyst or oxidant. Moreover, this method is also appropriate for the reaction of Ar2P(O)-H with a variety of amines, alcohols, and phenols.
Y. Tan, Y.-P. Han, Y. Zhang, H.-Y. Zhang, J. Zhao, S.-D. Yang, J. Org. Chem., 2022, 87, 3254-3264.
Simply heating secondary phosphine oxides and O-benzoylhydroxylamines in the presence of K2CO3 gives phosphinic amides in moderate to excellent yields under air. This method provides a practical and catalyst-free method for the synthesis of various synthetically valuable phosphinic amides.
R. Zhu, C. Pan, Z. Gu, Org. Lett., 2015, 17, 5862-5865.
Trimethylsilyl chloride as an activating agent enables a one-step synthesis of acyl phosphoramidates from a variety of functionalized acyl azides. This modified Staudinger reaction was further adapted to include in situ generation of acyl azides from a broad range of carboxylic acids and hydrazides.
I. Currie, B. E. Sleebs, Org. Lett., 2021, 23, 464-468.
Reductive radical cyclization of N-allyl-N-dimethylphosphinoyl-2-aminopropyl phenyl selenide using tris(trimethylsilyl)silane (TTMSS) / AIBN under UV irradiation gave the corresponding pyrrolidine in 74% yield and a cis/trans ratio of 10/1 which was superior to thermal cyclization.
D. Shanks, S. Berlin, M. Besev, H. Ottosson, L. Engman, J. Org. Chem., 2004, 69, 1487-1491.