N-P Bond Formation
Recent Literature
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.
A Tf2O-mediated direct amination of either P(O)-OH or P(O)-H reagents
with a variety of aliphatic or aromatic amines provides various phosphinamides
and phosphoramides. This protocol avoids the use of precious metals and toxic
reagents, proceeds under simple and mild conditions, and can be effectively
scaled up with similar efficiency.
D.-W. Shi, H.-Q. Yue, M. Li, J. Liu, C.-C. Wang, S.-D. Yang, B. Yang, J. Org. Chem., 2024, 89,
6729-6739.
A catalyst-free synthesis of phosphinic amides from hydroxyl amines and
chlorophosphines via P(III) to P(V) rearrangement involves the initial formation
of a R2N-O-PR2 species that undergoes homolysis of N-O
bonds and subsequent radical recombination.
F. Cheng, D. Li, J. Li, Y. Tang, Y. Wu, S. Xu, Org. Lett., 2023, 25,
2555-2559.
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.
A CuH-catalyzed reductive coupling of nitroarenes with phosphine oxides
produces a series of phosphamides in good yields and with good functional group
tolerance. Gram-scale synthesis and late-stage modifications are also
successfully conducted.
J. Tang, Z. Li, Q. Meng, L. Liu, T. Huang, C. Li, Q. Li, T. Chen, J. Org. Chem., 2024, 89,
7848-7858.
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.