Synthesis of N-protected O-hydroxyl-phenyl-α-aminophosphonic monoester

Article abstract of DOI:10.1080/10426500701796579

A series of N-protected O-hydroxylphenyl α-aminophosphonic monoesters were synthesized via three-component Mannich-type reactions of phosphoramides, aldehydes (ketones) and 2-chlorobenzo [1,3,2] dioxaphospholes under solvent free and catalyst-free conditions, followed by hydrolysis. It is an efficient and green method to the synthesis of N-phosphoramino O-hydroxyphenyl 1-aminoalkylphosphonic monoesters with high yields. Copyright Taylor & Francis Group, LLC.

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Phosphorus, Sulfur, and Silicon
and the Related Elements
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Synthesis of N-Protected
o-Hydroxyl-phenyl—α-
Aminophosphonic Monoester
Jianfeng Zhang a , Zhiwei Miao a , Zhanwei Cui a &
Ruyu Chen a
a State Key Laboratory of Elemento-Organic
Chemistry , Research Institute of Elemento-Organic
Chemistry, Nankai University , Tianjin, China
Published online: 20 Jun 2008.
To cite this article: Jianfeng Zhang , Zhiwei Miao , Zhanwei Cui & Ruyu Chen
(2008) Synthesis of N-Protected o-Hydroxyl-phenyl—α-Aminophosphonic Monoester,
Phosphorus, Sulfur, and Silicon and the Related Elements, 183:2-3, 679-680, DOI:
10.1080/10426500701796579
To link to this article: http://dx.doi.org/10.1080/10426500701796579
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Phosphorus, Sulfur, and Silicon, 183:679–680, 2008
Copyright © Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500701796579
Synthesis of N-Protected
o-Hydroxyl-phenyl—α-Aminophosphonic Monoester
Jianfeng Zhang, Zhiwei Miao, Zhanwei Cui,
and Ruyu Chen
State Key Laboratory of Elemento-Organic Chemistry, Research
Institute of Elemento-Organic Chemistry, Nankai University, Tianjin,
China
A series of N-protected O-hydroxylphenyl α-aminophosphonic monoesters were syn-
thesized via three-component Mannich-type reactions of phosphoramides, aldehydes
(ketones) and 2-chlorobenzo [1,3,2] dioxaphospholes under solvent free and catalyst-
free conditions, followed by hydrolysis. It is an efficient and green method to the syn-
thesis of N-phosphoramino O-hydroxyphenyl 1-aminoalkylphosphonic monoesters
with high yields.
Keywords α-aminophosphonic monoesters; Mannich-type reaction; no catalyst and
solvent-free
α−Aminophosphonic and phosphinic acids are the phosphorous ana-
logues of α-aminocarboxylic acids, and therefore have biological impor-
tance both in themselves and as building blocks for peptides.1 They have
acquired great attention in synthetic organic chemistry and a number
of synthetic methods have been developed during past two decades. Of
these methods, nucleophilic addition of phosphites to imines catalyzed
by a base or an acid is the most convenient one. A variety of metal
halides such as TiCl2, InCl3, TaCl5-SiO24, Mg(ClO4)5 have been used as
Lewis acid catalysts4in me3thylene chloride or othe2r organic solvent to
promote this addition. To avoid these disadvantages of the use of organic
solvents, a couple of modifications using montmorillonite clay6 and
alumina,7BiNO3·5H2O8 in dry media under microwave irradiation have
The authors thank the Committee of Science and Technology of Tianjln
(07JCZDJC04800) and Nankai University (J02044 to Z.W. Miao) for financial support.
Address correspondence to Zhiwei Miao State Key Laboratory of Elemento-Organic
Chemistry, Research Institute of Elemento-OrganicChemistry, Nankai University, Tian-
jin 300071, China. E-mail: miaozhiwei@nankai.edu.cn
679

680
J. Zhang et al.
TABLE I Preparation of α-aminophosphonic monoesters 4a–i
4
R1
R2
Yield (%)
4
R1
R2
Yield (%)
4a
4b
4c
4d
4e
p-Cl-C6H5
o-Cl-C6H5
p-Br-C6H5
o-Br-C6H5
C6H5
H
H
H
H
H
80
92
89
85
91
4f
4g
4h
4i
p-CH3O-C6H5
p-NO2-C6H5H
(CH2)5
CH3
—
H
H
—
CH3
—
90
93
84
87
—
—
been reported. In 2002, Ranu9reported a more practical green alterative
for the synthesis of α-aminophosphonates by a three-component con-
densation of carbonyl compounds (aldehydes and ketones), amines and
diethyl phosphite at 75–80◦C in neat without any solvent and catalyst.
We would like to disclose a practical and green method for the synthesis
of N-protected o-hydroxyl-phenyl-α-aminophosphonic monoester under
the condition of no catalyst and solvent-free (Scheme 1).
SCHEME 1
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