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Synlett

Volumn , Issue 7, 2007, Pages 1075-1078

Asymmetric intramolecular Michael reaction catalyzed by proline-derived small anilides

(3) Kikuchi, Makoto a Inagaki, Tomohiko a Nishiyama, Hisao a

a NAGOYA UNIVERSITY (Japan)

Author keywords

Cyclopentane; Michael reaction; Organocatalyst; Prolineanilide

Indexed keywords

ALDEHYDE DERIVATIVE; ANILIDE; PROLINE;

ARTICLE; ASYMMETRIC SYNTHESIS; CATALYSIS; CHEMICAL STRUCTURE; CHIRALITY; ISOMERIZATION; MICHAEL ADDITION;

EID: 34248158115 PISSN: 09365214 EISSN: None Source Type: Journal
DOI: 10.1055/s-2007-977421 Document Type: Article

Times cited : (20)

References (27)

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- Thiourea-catalyzed asymmetric intermolecular Michael reactions: (a) Okino, T.; Hoashi, Y.; Takemoto, Y. J. Am. Chem. Soc. 2003, 125, 12672.

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14
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- Pioneering work of the intramolecular Michael reaction mediated by stoichiometric amount of L-proline: (a) Kozikowski, A. P.; Mugrage, B. B. J. Org. Chem. 1989, 54, 2274.
- Pioneering work of the intramolecular Michael reaction mediated by stoichiometric amount of L-proline: (a) Kozikowski, A. P.; Mugrage, B. B. J. Org. Chem. 1989, 54, 2274.

15
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- The use of chiral amine: Hirai, Y.; Terada, T.; Yamazaki, T.; Momose, T. J. Chem. Soc., Perkin Trans. 1 1992, 509.
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16
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17
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18
- 34248183919
- Catalyst Preparation To a solution of N-Boc-protected proline (50 g, 0.23 mol) in anhyd DMF (250 mL, Et3N (39 mL, 0.28 mol) was added and the mixture was cooled to 0°C, then ethyl chloroformate (22 mL, 0.23 mol) was added dropwise over 30 min. The reaction temperature was maintained at 0°C for 40 min, and then diisopropylaniline (44 mL, 0.23 mol) was added at 0°C. The reaction mixture was stirred at 65°C for 14 h. The mixture was poured into H2O (150 mL) and crashed ice (150 mL, The precipitated solid was filtered and dried in air. A part of the crude N-Boc-protected anilide (50 g) was dissolved in CHCl3 (100 mL) and TFA (98, 100 mL) was added at r.t. The reaction mixture was stirred at 50°C for 2 h. The solvent was removed and the pH of the residue was adjusted to 8-9 by the addition of aq NaOH 2 N, the product was extracted with CHCl3, and dried over MgSO4. After removal of the solven
- 2O: C, 74.41; H, 9.55; N, 10.21. Found: C, 74.30; H, 9.68; N, 10.10.

19
- 0345359331
- 2O furnished lower reactivity in moderate enantioselectivity (catalyst 1a, 5 h, 92%, cis/ trans = 44:56, 81% ee for cis, 62% ee for trans). The advantage of additives in aldol reaction, see: (a) Mase, N.; Tanaka, F.; Barbas, C. F. III Org. Lett. 2003, 5, 4369.
- 2O furnished lower reactivity in moderate enantioselectivity (catalyst 1a, 5 h, 92%, cis/ trans = 44:56, 81% ee for cis, 62% ee for trans). The advantage of additives in aldol reaction, see: (a) Mase, N.; Tanaka, F.; Barbas, C. F. III Org. Lett. 2003, 5, 4369.

20
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- (b) Pihko, P. M.; Laurikainen, K. M.; Usano, A.; Nyberg, A. I.; Kaavi, J. A. Tetrahedron 2006, 62, 317.
- (2006) Tetrahedron , vol.62 , pp. 317
- Pihko, P.M.¹ Laurikainen, K.M.² Usano, A.³ Nyberg, A.I.⁴ Kaavi, J.A.⁵

21
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- For the important correspondences about the water effect, see: c
- For the important correspondences about the water effect, see: (c) Brogan, A. P.; Dickerson, T. J.; Janda, K. D. Angew. Chem. Int. Ed. 2006, 45, 8100.
- (2006) Angew. Chem. Int. Ed , vol.45 , pp. 8100
- Brogan, A.P.¹ Dickerson, T.J.² Janda, K.D.³

22
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- Chem. Int. Ed, and references cited therein
- (d) Hayashi, Y. Angew. Chem. Int. Ed. 2006, 45, 8103; and references cited therein.
- (2006) Angew , vol.45 , pp. 8103
- Hayashi, Y.¹

23
- 34248158835
- General Procedure for Intramolecular Michael Reaction To a mixture of anilide 1 (0.06 mmol, 30 mol, and the corresponding formyl enone 2 (0.2 mmol) were added CHCl3 (2.5 mL, H2O (50 μL) and AcOH (0.06 mmol, 30 mol, at 30°C. The mixture was stirred at 30°C until TLC indicated complete reaction. The reaction was quenched at r.t. with H2O (1 mL) and extracted with Et2O (3 x 3 mL, The combined organic extracts were washed with brine, dried over Na 2SO4, filtered and concentrated in vacuo. After purification by column chromatography (silica gel, hexane-Et2O) furnished analytically pure 3a-c. Compound cis-3a: Chiral GC analysis (SUPELCO/β-DEX 325, 95°C, 60 kPa H2 as carrier gas, tR(minor, 88.0 min, tR(major, 89.1 min. 1H NMR (300 Mz, CDCl3, δ, 9.70 d, J, 2.4 Hz
- 3): δ = 214.4, 203.1, 57.8, 44.0, 41.5, 36.5, 33.1, 26.9, 26.4, 24.9.

24
- 34248171580
- The same dr shift during the extended reaction time has been reported by Hayashi's group
- The same dr shift during the extended reaction time has been reported by Hayashi's group. They have succeeded in the isomerization from cis- to trans-isomer under the basic condition without loss of enantiopurity; see ref. 10.
- They have succeeded in the isomerization from cis- to trans-isomer under the basic condition without loss of enantiopurity

25
- 34248194828
- It is assumed that this isomerization occurred through the diastereoselective protonation or hydrolysis of enamine or iminium generated from further reaction between product aldehyde 3 and catalyst. However, it cannot be seen that the isomerization occurred via the same intermediate enamine or iminium in the cyclization reaction, because the dr in the short reaction time is almost none selective e.g. entry 1, Table 3, Therefore we consider that this isomerization occurred via the enolate intermediate forming from the aldehyde 3
- It is assumed that this isomerization occurred through the diastereoselective protonation or hydrolysis of enamine or iminium generated from further reaction between product aldehyde 3 and catalyst. However, it cannot be seen that the isomerization occurred via the same intermediate enamine or iminium in the cyclization reaction, because the dr in the short reaction time is almost none selective (e.g. entry 1, Table 3). Therefore we consider that this isomerization occurred via the enolate intermediate forming from the aldehyde 3.

26
- 27544489337
- The absolute stereochemistry of 3b was determined by comparison of its HPLC analysis reported by Hayashi et al., see ref. 10 and: Yang, J. W.; Fonseca, M. T. H.; List, B. J. Am. Chem. Soc. 2005, 127, 15036.
- (a) The absolute stereochemistry of 3b was determined by comparison of its HPLC analysis reported by Hayashi et al., see ref. 10 and: Yang, J. W.; Fonseca, M. T. H.; List, B. J. Am. Chem. Soc. 2005, 127, 15036.

27
- 34248207082
- in the light of the reaction mechanism, we speculate that the other ketoaldehydes 3a and 3c have the same absolute configuration S at C2 (Figure 2).
- (b) in the light of the reaction mechanism, we speculate that the other ketoaldehydes 3a and 3c have the same absolute configuration S at C2 (Figure 2).

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