Abstract
A facile stereoselective synthesis of cyclopropylphosphonates
from the reaction of inexpensive α-chlorophosphonates with
alkyl acrylates in the presence of sodium hydride is reported. Reaction
with dimethyl maleate or fumarate also leads to cyclopropyl-substituted
phosphonates. These reactions take place via Michael addition of
acrylate, dimethyl maleate, or fumarate to the phosphonate carbanion,
followed by expulsion of the chloride ion.
Key words
phosphonates - Michael addition - acrylates - diastereomers - cyclopropanes
References
1 Zwierzak A.
Can.
J. Chem.
1967,
45:
2501
2a Kumaraswamy S.
Selvi RS.
Kumara Swamy KC.
Synthesis
1997,
207
2b Kumaraswamy S.
Kumara Swamy KC.
Tetrahedron
Lett.
1997,
38:
2183
2c Praveen Kumar K.
Muthiah C.
Kumaraswamy S.
Kumara Swamy KC.
Tetrahedron
Lett.
2001,
42:
3219
2d Muthiah C.
Senthil Kumar K.
Vittal JJ.
Kumara Swamy KC.
Synlett
2002,
1787
2e Chakravarty M.
Srinivas B.
Muthiah C.
Kumara Swamy KC.
Synthesis
2003,
2368
2f Kumara Swamy KC.
Kumaraswamy S.
Senthil
Kumar K.
Muthiah C.
Tetrahedron
Lett.
2005,
46:
3347
3a Muthiah C.
Praveen Kumar K.
Kumaraswamy S.
Kumara Swamy KC.
Tetrahedron
1998,
54:
14315
3b Muthiah C.
Praveen Kumar K.
Aruna Mani C.
Kumara Swamy KC.
J. Org. Chem.
2000,
65:
3733
3c Senthil Kumar K.
Kumara Swamy KC.
J. Organomet. Chem.
2001,
637-639:
616
3d Chakravarty M.
Kumara Swamy KC.
J. Org. Chem.
2006,
71:
9128
3e Kumara Swamy KC.
Balaraman E.
Kumar NS.
Tetrahedron
2006,
62:
10152
4 Hanessian S.
Cantin L.-D.
Roy S.
Andreotti D.
Gomtsyan A.
Tetrahedron
Lett.
1997,
38:
1103
5 Yuan C.
Li C.
Ding Y.
Synthesis
1991,
854
6a Sitachitta N.
Gerwick WH.
J.
Nat. Prod.
1998,
61:
681
6b Cao B.
Xiao D.
Joullie MM.
Org.
Lett.
1999,
1:
1799
6c Esposito A.
Piras PP.
Ramazzotti D.
Taddei M.
Org. Lett.
2001,
3:
3273
6d Ono S.
Ogawa K.
Yamashita K.
Yamamoto T.
Kazuta Y.
Matsuda A.
Shuto S.
Chem.
Pharm. Bull.
2002,
50:
966
6e Kazuta Y.
Matsuda A.
Shuto S.
J.
Org. Chem.
2002,
67:
1669
6f Frydman B.
Blokhin AV.
Brummel S.
Wilding G.
Maxuitenko Y.
Sarkar A.
Bhattacharya S.
Church D.
Reddy VK.
Kink JA.
Marton LJ.
Valasinas A.
Basu HS.
J.
Med. Chem.
2003,
46:
4586
6g Janjic JM.
Mu Y.
Kendall C.
Stephenson CRJ.
Balachandran R.
Raccor BS.
Lu Y.
Zhu G.
Xie W.
Wipf P.
Day BW.
Bioorg.
Med. Chem.
2005,
13:
157
6h Reichelt A.
Martin SF.
Acc. Chem. Res.
2006,
39:
433
7a Yamaguchi M.
Tsukamoto Y.
Hayashi A.
Minami T.
Tetrahedron
Lett.
1990,
31:
2423
7b Haynes RK.
Stokes JP.
Hambley TW.
J. Chem. Soc., Chem. Commun.
1991,
58
7c Haynea RK.
Vonwiller SC.
Hambley TW.
J. Org. Chem.
1989,
54:
5162
7d Hanessian S.
Gomtsyan A.
Payne A.
Herve Y.
Beaudoin S.
J.
Org. Chem.
1993,
58:
5032
8 We have utilized the reaction of inexpensive
PBr3 with α-hydroxyphosphonates also to prepare
a series of 2-[aryl(bromo)methyl]-5,5-dimethyl-1,3,2-dioxaphosphinane 1-oxides
(aryl = phenyl, 4-methylphenyl, 4-chlorophenyl, 4-bromophenyl);
some of these compound have been previously reported.
[²a
9 Pavan Kumar KVP.
PhD Thesis
University of Hyderabad;
India:
2006.
10 All data has been deposited at the
Cambridge database. We believe that such information will be useful,
in case these compounds are pharmacologically active.
11 Perrin DD.
Armarego WLF.
Perrin DR.
Purification of
Laboratory Chemicals
Pergamon;
Oxford:
1986.
12a Sheldrick
G. M., SHELX-97, University of Göttingen, Germany, 1997.
12b Sheldrick G. M., SADABS,
Siemens Area Detector Absorption Correction, University of Göttingen,
Germany, 1996.
12c Sheldrick G. M., SHELXTL NT, version 5.10; Bruker AXS, Analytical
X-ray System, WI, 1999.
