Regioselective Allylic Amination of the Baylis-Hillman Adducts: An Easy and Practical Access to the Baylis-Hillman Adducts of N-Tosylimines

Jae Nyoung Kim; Hong Jung Lee; Ka Young Lee; Ji Hyeon Gong

doi:10.1055/s-2002-19360

LETTER

Regioselective Allylic Amination of the Baylis-Hillman Adducts: An Easy and Practical Access to the Baylis-Hillman Adducts of N-Tosylimines

Jae Nyoung Kim*, Hong Jung Lee, Ka Young Lee, Ji Hyeon Gong
Department of Chemistry and Institute of Basic Science, Chonnam National University, Kwangju 500-757, Korea
Fax: +82(62)5303381; e-Mail: kimjn@chonnam.chonnam.ac.kr;

Abstract

Alle Artikel dieser Rubrik

Abstract

The reaction of the in situ generated DABCO salt of Baylis-Hillman acetate and tosylamide in aqueous THF gave the Baylis-Hillman adduct of N-tosylimine in good yield. The method seems very simple and practical for the preparation of Baylis-Hillman adduct of N-tosylimine.

Key words

Baylis-Hillman adducts - N-tosylimine - DABCO - allylic amination - deracemization

Volltext

Referenzen

References

<A NAME="RY21801ST-1A">1a</A> Ciganek E. Organic Reactions Vol. 51: John Wiley and Sons; New York: 1997. p.201

<A NAME="RY21801ST-1B">1b</A> Drewes SE. Roos GHP. Tetrahedron 1988, 44: 4653

<A NAME="RY21801ST-1C">1c</A> Basavaiah D. Rao PD. Hyma RS. Tetrahedron 1996, 52: 8001

<A NAME="RY21801ST-2A">2a</A> Perlmutter P. Teo CC. Tetrahedron Lett. 1984, 25: 5951

<A NAME="RY21801ST-2B">2b</A> Bertenshaw S. Kahn M. Tetrahedron Lett. 1989, 30: 2731

<A NAME="RY21801ST-2C">2c</A> Kundig EP. Xu LH. Schnell B. Synlett 1994, 413

<A NAME="RY21801ST-2D">2d</A> Richter H. Jung G. Tetrahedron Lett. 1998, 39: 2729

<A NAME="RY21801ST-2E">2e</A> Yamamoto K. Takagi M. Tsuji J. Bull. Chem. Soc. Jpn. 1988, 61: 319

Quite recently Balan and Adolfsson have reported the facile synthesis of the Baylis-Hillman adducts of N-tosylimines through a three-component reaction of arylaldehydes, tosylamide and a Michael acceptor, see: (f) Balan D. Adolfsson H. J. Org. Chem. 2001, 66: 6498

<A NAME="RY21801ST-3A">3a</A> Kim JN. Lee HJ. Lee KY. Kim HS. Tetrahedron Lett. 2001, 42: 3737

<A NAME="RY21801ST-3B">3b</A> Lee HJ. Kim HS. Kim JN. Tetrahedron Lett. 1999, 40: 4363

<A NAME="RY21801ST-3C">3c</A> Lee HJ. Seong MR. Kim JN. Tetrahedron Lett. 1998, 39: 6223

<A NAME="RY21801ST-3D">3d</A> Genisson Y. Massardier C. Gautier-Luneau I. Greene AE. J. Chem. Soc., Perkin Trans. 1 1996, 2869

<A NAME="RY21801ST-3E">3e</A> Li G. Kim SH. Wei H.-X. Tetrahedron 2000, 56: 719

<A NAME="RY21801ST-3F">3f</A> Kundig EP. Xu L.-H. Romanens P. Tetrahedron Lett. 1995, 36: 4047

<A NAME="RY21801ST-3G">3g</A> Takagi M. Yamamoto K. Tetrahedron 1991, 47: 8869

For the synthesis of N-tosylimines, see:

<A NAME="RY21801ST-4A">4a</A> Jennings WB. Lovely CJ. Tetrahedron 1991, 47: 5561

<A NAME="RY21801ST-4B">4b</A> Trost BM. Marrs C. J. Org. Chem. 1991, 56: 6468

<A NAME="RY21801ST-4C">4c</A> Boger DL. Corbett WL. J. Org. Chem. 1992, 57: 4777

<A NAME="RY21801ST-4D">4d</A> Boger DL. Corbett WL. Curran TT. Kasper AM. J. Am. Chem. Soc. 1991, 113: 1713

<A NAME="RY21801ST-4E">4e</A> Sisko J. Weinreb SM. Tetrahedron Lett. 1989, 30: 3037

<A NAME="RY21801ST-4F">4f</A> Sisko J. Weinreb SM. J. Org. Chem. 1990, 55: 393

<A NAME="RY21801ST-4G">4g</A> Georg GI. Harriman GCB. Peterson SA. J. Org. Chem. 1995, 60: 7366

<A NAME="RY21801ST-4H">4h</A> Love BE. Raje PS. Williams TCII. Synlett 1994, 493

<A NAME="RY21801ST-5A">5a</A> Im YJ. Kim JM. Mun JH. Kim JN. Bull. Korean Chem. Soc. 2001, 22: 349

<A NAME="RY21801ST-5B">5b</A> Drewes SE. Horn MM. Ramesar N. Synth. Commun. 2000, 30: 1045

<A NAME="RY21801ST-5C">5c</A> Basavaiah D. Kumaragurubaran N. Tetrahedron Lett. 2001, 42: 477

<A NAME="RY21801ST-5D">5d</A> Basavaiah D. Kumaragurubaran N. Sharada DS. Tetrahedron Lett. 2001, 42: 85

Cyclohexene derivatives were obtained as diastereomeric mixtures from 1e and 1h via the elimination of acetic acid and concomitant Diels-Alder reaction. Diethyl 4-(1-hexenyl)-3-butyl-1-cyclohexene-1,4-dicarboxylate (for 1e) and 4-(1-hexenyl)-3-butyl-1,4-dicyano-1-cyclohexene (for 1h) were isolated in 43% and 48%, respectively, as an oil. For such reactions, see:

<A NAME="RY21801ST-6A">6a</A> Poly W. Schomburg D. Hoffmann HMR. J. Org. Chem. 1988, 53: 3701

<A NAME="RY21801ST-6B">6b</A> Hoffmann HMR. Eggert U. Poly W. Angew. Chem., Int. Ed. Engl. 1987, 26: 1015

<A NAME="RY21801ST-6C">6c</A> Hoffman HMR. Weichert A. Slawin AMZ. Williams DJ. Tetrahedron 1990, 46: 5591

Other nucleophiles can be used in the reaction such as phenols and primary nitroalkanes, which have the similar pK_a values as that of tosylamide.

<A NAME="RY21801ST-8">8</A> Trost BM. Tsui H.-C. Toste FD. J. Am. Chem. Soc. 2000, 122: 3534

Typical Procedure for the Formation of 3a: To a stirred solution of the Baylis-Hillman acetate 1a (496 mg, 2.0 mmol) in aq THF (10 mL, H₂O-THF, 1:1) was added DABCO (270 mg, 2.4 mmol) and stirred at r.t. for 10 min. To the reaction mixture p-toluenesulfonamide (345 mg, 2.0 mmol) was added and the whole mixture was stirred at 60-70 °C for 48 h. After the usual workup process and column chromatography (SiO₂, hexane/ether, 1:1), 3a was obtained as a white solid, 540 mg (75%); mp 100-101 °C (ref. [2a] 90-92 °C); IR (CH₂Cl₂): 3289, 1716, 1327, 1161 cm^-1; ¹H NMR (CDCl₃): δ = 1.14 (t, J = 7.2 Hz, 3 H), 2.41 (s, 3 H), 4.04 (q, J = 7.2 Hz, 2 H), 5.30 (d, J = 9.0 Hz, 1 H), 5.65 (d, J = 9.0 Hz, 1 H), 5.81 (s, 1 H), 6.21 (s, 1 H), 7.13-7.69 (m, 9 H); ¹³C NMR (CDCl₃): δ = 13.89, 21.46, 59.12, 60.97, 126.44, 127.21, 127.51, 127.66, 128.49, 129.44, 137.75, 138.75, 138.84, 143.29, 165.27; CIMS: m/z (%) = 189(92), 204(100), 205(15), 360(1) [MH⁺]. Anal. Calcd for C₁₉H₂₁NO₄S: C, 63.49; H, 5.89; N, 3.90. Found: C, 63.32; H, 5.91; N, 3.94.