Subscribe to RSS
DOI: 10.1055/s-2005-863723
Phosphomolybdic Acid-Catalyzed Efficient Three-Component Reaction: A Facile Synthesis of Protected Homoallylic Amines
Publication History
Publication Date:
09 March 2005 (online)
![](https://www.thieme-connect.de/media/synlett/200505/lookinside/thumbnails/10.1055-s-2005-863723-1.jpg)
Abstract
A new and efficient phosphomolybdic acid (H3PMo12O40)-catalyzed three-component reaction of aldehydes, carbamate and allyltrimethylsilane to yield the corresponding protected homoallylic amines in good yields is described.
Key words
phosphomolybdic acid - three-component reaction - homoallylic amines - heteropolyacid
- For a review, see:
-
1a
Yamamoto Y.Asao N. Chem. Rev. 1993, 93: 2207 -
1b
Wright DL.Schulte JP.Page MA. Org. Lett. 2000, 2: 1847 -
1c
Ovaa H.Stragies R.van der Marel GA.van Boom JH.Blechert S. Chem. Commun. 2000, 16: 1501 -
1d
Hunt JCA.Laurent P.Moody CJ. Chem. Commun. 2000, 18: 1771 -
1e
Hiemstra H.Speckamp WN. In Comprehensive Organic Synthesis Vol. 2:Fleming I. Pergamon Press; Oxford: 1991. p.1047 -
1f
Voigtmann V.Blechert S. Synthesis 2000, 893 - For recent reviews, see:
-
2a
Kleinman EF.Volkmann RA. In Comprehensive Organic Synthesis Vol. 2:Trost BM.Fleming I. Pergamon; Oxford: 1991. p.975 -
2b
Bloch R. Chem. Rev. 1998, 98: 1407 -
2c
Yamamoto Y. Acc. Chem. Res. 1987, 20: 243 -
3a
Yadav JS.Reddy BVS.Reddy PSR.Rao MS. Tetrahedron Lett. 2002, 43: 6245 -
3b
Aspinall HC.Bisset JS.Greeves N.Levin D. Tetrahedron Lett. 2002, 43: 323 -
3c
Chaudary BM.Chidara S.Sekhar CVR. Synlett 2002, 1694 -
3d
Akiyama T.Onuma Y. J. Chem. Soc., Perkin Trans. 1 2002, 1157 -
3e
Nakamura K.Nakamura H.Yamamoto Y. J. Org. Chem. 1999, 64: 2614 -
3f
Kobayashi S.Busujima T.Nagayama S. Chem. Commun. 1998, 19 -
3g
Nakamura H.Nakamura K.Yamamoto Y. J. Am. Chem. Soc. 1998, 120: 4242 -
3h
Akiyama T.Iwai J. Synlett 1998, 273 -
3i
Kobayashi S.Nagayama S. J. Am. Chem. Soc. 1997, 119: 10049 -
4a
Veenstra SJ.Schmid P. Tetrahedron Lett. 1997, 38: 997 -
4b
Niimi L.Serita K.Hiraoka S.Yokozawa T. Tetrahedron Lett. 2000, 41: 7075 -
4c
Billet M.Klotz P.Mann A. Tetrahedron Lett. 2001, 42: 631 -
4d
Ollevier T.Ba T. Tetrahedron Lett. 2003, 44: 9003 -
4e
Phukan P. J. Org. Chem. 2004, 69: 4005 -
5a
Larsen SD.Grieco PA.Fobare WF. J. Am. Chem. Soc. 1986, 108: 3512 -
5b
Grieco PA.Bahsas A. J. Org. Chem. 1987, 52: 1378 -
5c
Masuyama Y.Tosa J.Kurusu Y. Chem. Commun. 1999, 1075 -
5d
Masuyama Y.Iwai J.Onuma Y.Kagoshima H. Chem. Commun. 1999, 2191 -
5e
Choucair B.Leon H.Mire M.-A.Lebreton C.Mosset P. Org. Lett. 2000, 2: 1851 -
5f
Sugiura M.Hirano K.Kobayashi S. J. Am. Chem. Soc. 2004, 126: 7182 -
6a
Greene TW.Wuts PGM. Protective Groups in Organic Synthesis 3rd ed.: Wiley; New York: 1999. -
6b
Kocienski PJ. Protective Groups Georg Thieme; Stuttgart: 1994. - 7
Clark JH. Acc. Chem. Res. 2002, 35: 791 -
8a
Kozhevnikov IV. Chem. Rev. 1998, 98: 171 -
8b
Mizuno N.Misono M. Chem. Rev. 1998, 98: 199 -
8c
Misono M.Ono I.Koyano G.Aoshima A. Pure Appl. Chem. 2000, 72: 1305 -
8d
Wilson K.Clark JH. Pure Appl. Chem. 2000, 72: 1313 -
9a
Kumar GDK.Baskaran S. Synlett 2004, 1719 -
9b
Kumar GDK.Baskaran S. Chem. Commun. 2004, 1026 -
10a
Bruhaspathy M.Bhattacharyya S.Williamson JS. Tetrahedron 2004, 60: 1463 -
10b
Bhattacharyya S.Neidigh KA.Avery MA.Williamson JS. Synlett 1999, 1781 -
10c
Neidigh KA.Avery MA.Williamson JS.Battacharyya S. J. Chem. Soc., Perkin Trans. 1 1998, 2527 -
10d
Bhattacharyya S.Chatterjee A.Williamson JS. Synlett 1995, 1079
References
Spectroscopic data for the selected products:
Table 1, Entry 3: 1H NMR (400 MHz, CDCl3): δ = 7.65 (d, J = 7.6 Hz, 2 H), 7.45 (t, J = 7.6 Hz, 1 H), 7.34 (t, J = 7.6 Hz, 2 H), 7.18-7.14 (m, 3 H), 7.07-7.04 (m, 2 H), 5.55-5.47 (m, 1 H), 5.08-5.04 (m, 2 H), 4.93 (br s, 1 H), 4.42-4.40 (m, 1 H), 2.46 (t, J = 5.2 Hz, 2 H). 13C NMR (100 MHz, CDCl3): δ = 140.6, 140.3, 133.2, 132.2, 128.7 (2 C), 128.3 (2 C), 127.4, 127.0 (2 C), 126.6 (2 C), 118.9, 57.6, 41.8. IR (neat): 3276, 2949, 2331, 1319, 1161, 753 cm-1. HRMS (ESI): m/z calcd for C16H17NO2S: 310.0877 [M + Na]+; found: 310.0870.
Table 2, Entry 8: 1H NMR (500 MHz, CDCl3): δ = 7.35-7.26 (m, 5 H), 7.18 (d, J = 7.5 Hz, 2 H), 6.85 (d, J = 8.5 Hz, 2 H), 5.67-5.61 (m, 1 H), 5.30-5.10 (m, 5 H), 4.85 (br s, 1 H), 2.56 (br s, 1 H), 1.05 (s, 9 H), 0.26 (s, 6 H). 13C NMR (125 MHz, CDCl3): δ = 155.6, 154.6, 136.5, 134.7, 133.9, 128.4 (2 C), 128.0 (2 C), 127.3 (2 C), 119.9 (3 C), 118.1, 66.9, 54.5, 41.3, 26.1 (3 C), 18.6, -3.8 (2 C). IR (neat): 3325, 2929, 1698, 1509, 1256, 914 cm-1. HRMS (ESI): m/z calcd for C24H33NO3Si: 434.2127 [M + Na]+; found: 434.2120.
Table 2, Entry 9: 1H NMR (500 MHz, CDCl3): δ = 7.41-7.34 (m, 5 H), 7.24 (dd, J = 2.0, 6.0 Hz, 2 H), 7.16 (d, J = 8.0 Hz, 1 H), 7.01 (t, J = 7.5 Hz, 1 H), 5.80-5.70 (m, 2 H), 5.30 (s, 2 H), 5.17-5.08 (m, 5 H), 3.52 (s, 3 H), 2.64 (t, J = 6.0 Hz, 2 H). 13C NMR (125 MHz, CDCl3): δ = 155.5, 154.2, 136.6, 134.5, 130.2, 128.4, 128.3, 128.1, 128.0, 127.9, 121.7 (3 C), 117.7, 114.2, 94.3, 66.8, 56.4, 52.2, 40.3. IR (neat): 3342, 2954, 1716, 1492, 1233, 995 cm-1. HRMS (ESI): m/z calcd for C20H23NO4: 364.1524 [M + Na]+; found: 364.1517.
Table 2, Entry 12: 1H NMR (400 MHz, CDCl3): δ = 7.92 (d, J = 8.0 Hz, 2 H,), 7.43-7.34 (m, 7 H), 5.66-5.58 (m, 1 H), 5.14-5.02 (m, 4 H), 4.85 (br s, 1 H), 2.58 (s, 5 H). 13C NMR (100 MHz, CDCl3): δ = 197.8, 155.9, 136.2, 133.4, 128.7 (3 C), 128.5 (2 C), 128.1 (2 C), 128.0 (2 C), 126.5 (2 C), 118.7, 116.5, 66.8, 40.8, 26.5. IR (neat): 3329, 3065, 1708, 1681, 1530, 1219, 698 cm-1. HRMS (ESI): m/z calcd for C20H21NO3: 346.1417 [M + Na]+; found: 346.1409.