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Synlett 2017; 28(02): 265-269
DOI: 10.1055/s-0036-1588618
DOI: 10.1055/s-0036-1588618
letter
Trityl Cation Catalyzed Intramolecular Carbonyl-Ene Cyclization and [2+2] Cycloaddition
Weitere Informationen
Publikationsverlauf
Received: 19. August 2016
Accepted after revision: 12. September 2016
Publikationsdatum:
06. Oktober 2016 (online)
![](https://www.thieme-connect.de/media/synlett/201702/lookinside/thumbnails/st-2016-u0539-l_10-1055_s-0036-1588618-1.jpg)
Abstract
An unprecedented metal-free catalytic system composed of trityl halides and thioureas has been found to be a convenient source for the generation of trityl cation species, and this cooperative catalytic system was proved to be highly effective for intramolecular carbonyl-ene cyclization and [2+2] cycloadditions.
Key words
trityl cation catalysis - intramolecular carbonyl-ene - intramolecular [2+2] cycloaddition - thiourea catalystSupporting Information
- Supporting information for this article is available online at http://dx.doi.org/10.1055/s-0036-1588618.
- Supporting Information
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References and Notes
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- 24 Typical Procedure for the Carbonyl-Ene Cyclization of (–)-Citronellal (Table 1, Entry 1) A mixture of (–)-citronellal (1, 77 mg, 0.5 mmol), thiourea (TU, 25 mg, 0.05 mmol), and trityl bromide (I, 16 mg, 0.05 mmol) in anhydrous CH2Cl2 (5 mL) was stirred at r.t., and the reaction progress was monitored by TLC. After completion, the mixture was concentrated in vacuo, and the residue was purified by column chromatography (eluted with hexane–Et2O, 9:1) to give 2 (45 mg, 58.4%) and 3 (29 mg, 37.7%). (+)-Isopulegol (2) 18i,25 Colorless liquid; Rf = 0.30 (hexane–EtOAc, 5:1). FTIR (neat): ν = 3408, 1645, 1455, 1375 cm–1. 1H NMR (500 MHz, CDCl3): δ = 0.87–1.02 (m, 2 H), 0.95 (d, J = 6.5 Hz, 3 H), 1.32 (dq, J = 11.5, 3.5 Hz, 1 H), 1.46–1.55 (m, 1 H), 1.66–1.70 (m, 2 H), 1.71 (s, 3 H), 1.89 (ddd, J = 12.5, 10.0, 3.0 Hz, 2 H), 2.04 (dt, J = 12.0, 3.0 Hz, 1 H), 3.46 (dt, J = 10.0, 4.0 Hz, 1 H), 4.86 (s, 1 H), 4.90 (s, 1 H). 13C NMR (125.8 MHz, CDCl3): δ = 19.18, 22.22, 29.64, 31.45, 34.33, 42.64, 54.15, 70.35, 112.84, 146.63. (–)-Neoisopulegol (3) 18i,25 Colorless liquid; Rf = 0.41 (hexane–EtOAc, 5:1). FTIR (neat): ν = 3453, 1644, 1455, 1446, 1390, 1374 cm–1. 1H NMR (500 MHz, CDCl3): δ = 0.89 (d, J = 6.0 Hz, 3 H), 0.95 (dq, J = 12.0, 3.5 Hz, 2 H), 1.13 (t, J = 13.0 Hz, 1 H), 1.43–1.47 (m, 1 H), 1.48 (s, 1 H), 1.67–1.77 (m, 2 H), 1.79 (s, 3 H), 1.98 (d, J = 12.0 Hz, 2 H), 3.99 (s, 1 H), 4.79 (s, 1 H), 4.95 (s, 1 H). 13C NMR (125.8 MHz, CDCl3): δ = 22.23, 22.77, 23.94, 25.81, 34.76, 40.91, 48.40, 66.32, 111.29, 147.34. General Procedure for the High-Pressure-Promoted Reaction of Unsaturated Carbonyl Compounds or Activated Dienes All high-pressure reactions were performed in a Hikari-Koatsu HR-15-B3 apparatus, which is designed for pressures up to 1.0 GPa. A mixture of aldehyde or diene (0.2 mmol), thiourea (TU, 10 mg, 0.02 mmol), and trityl bromide (I, 6.5 mg, 0.02 mmol) in anhydrous CH2Cl2 (2 mL) was reacted at 1.0 GPa and at r.t. for the period shown in Tables 2 and 3. After releasing the pressure, the mixture was concentrated in vacuo, and the residue was purified by column chromatography (eluted with hexane–Et2O). trans-2-(1-Methylethenyl)cyclohexanol (trans-6, Table 2, Entry 8) 26 Colorless liquid; Rf = 0.28 (hexane–EtOAc, 5:1). FTIR (neat): ν = 3419, 1645, 1449, 1277 cm–1. 1H NMR (400 MHz, CDCl3): δ = 1.13–1.30 (m, 5 H), 1.61 (br s,1 H), 1.65 (s, 3 H), 1.69–1.73 (m, 1 H), 1.84–1.90 (m, 2 H), 1.98–2.02 (m, 1 H), 3.36 (dt, J = 9.6, 4.0 Hz, 1 H), 4.79 (s, 1 H), 4.83 (s, 1 H). 13C NMR (100 MHz, CDCl3): δ = 19.14, 24.82, 25.61, 30.12, 34.03, 54.52, 70.66, 112.78, 146.60. cis-2-(1-Methylethenyl)cyclohexanol (cis-6, Table 2, Entry 8) 26 Colorless liquid; Rf = 0.35 (hexane–EtOAc, 5:1). FTIR (neat): ν = 3447, 1643, 1446, 1374 cm–1. 1H NMR (400 MHz, CDCl3): δ = 1.27 (tq, J = 12.4, 3.2 Hz, 2 H), 1.42–1.52 (m, 4 H), 1.61 (tq, J = 13.6, 3.2 Hz, 1 H), 1.67 (dq, J = 13.6, 3.2 Hz, 1 H), 1.79 (s, 3 H), 2.01 (dt, J = 15.6, 2.0 Hz, 2 H), 3.98 (br s, 1 H), 4.78 (s, 1 H), 4.95 (s, 1 H). 13C NMR (100 MHz, CDCl3): δ = 19.68, 22.65, 23.85, 25.93, 32.15, 48.59, 65.75, 111.23, 147.53. Compound 12 (Table 3, Entry 1) Colorless oil; Rf = 0.46 (hexane–Et2O, 10:1). FTIR (KBr): ν = 1751, 1732, 1644, 1498, 1456, 1376 cm–1. 1H NMR (500 MHz, CDCl3): δ = 0.82 (d, J = 6.5 Hz, 3 H), 0.88 (dq, J = 12.5, 3.5 Hz, 1 H), 1.06 (q, J = 12.5 Hz, 1 H), 1.30–1.39 (m, 2 H), 1.59 (s, 3 H), 1.60–1.72 (m, 3 H), 2.04 (dt, J = 11.5, 3.0 Hz, 1 H), 2.11 (tt, J = 11.5, 3.5 Hz, 1 H), 3.61 (d, J = 3.5 Hz, 1 H), 4.64 (s, 1 H), 4.70 (s, 1 H), 5.12(5) (ABq, J AB = 12.0 Hz, 2 H), 5.13(0) (ABq, J AB = 12.0 Hz, 2 H), 7.26–7.35 (m, 10 H). 13C NMR (125.8 MHz, CDCl3): δ = 18.83, 22.39, 32.20, 32.63, 34.55, 36.41, 39.95, 48.53, 53.28, 66.62, 66.82, 112.55, 128.11 (×2), 128.20, 128.26, 128.45 (×4), 128.50 (×2), 135.50, 135.53, 147.42, 168.31, 169.48. HRMS: m/z calcd for C27H32O4: 420.2301; found: 420.2302. Compound 13 (Table 3, Entry 1) Colorless oil; Rf = 0.53 (hexane–Et2O, 10:1). FTIR (KBr): ν = 1732, 1456, 1242 cm–1. 1H NMR (500 MHz, CDCl3): δ = 0.86 (d, J = 6.5 Hz, 3 H), 0.94–1.06 (m, 2 H), 1.03 (s, 3 H), 1.17 (dq, J = 12.0, 3.5 Hz, 1 H), 1.25 (s, 3 H), 1.51–1.55 (m, 2 H), 1.68–1.73 (m, 2 H), 1.97 (dt, J = 12.0, 2.5 Hz, 1 H), 2.26 (dt, J = 12.0, 2.5 Hz, 1 H), 5.10 (ABq, J AB = 12.5 Hz, 2 H), 5.11 (ABq, J AB = 12.5 Hz, 2 H), 7.22–7.30 (m, 10 H). 13C NMR (125.8 MHz, CDCl3): δ = 20.12, 22.63, 23.88, 26.26, 33.23, 34.89, 35.59, 43.65, 46.87, 47.92, 64.08, 66.23, 66.39, 127.91, 128.00, 128.04, 128.12 (×2), 128.37, 128.39 (×4), 135.79 (×2), 168.96, 170.09. Anal. Calcd (%) for C27H32O4: C, 77.11; H, 7.67. Found: C, 76.71; H, 7.68.
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Reviews:
For recent reviews of the Mukaiyama aldol reaction, see:
Reviews:
Reviews:
For previous examples of high-pressure-promoted carbonyl-ene reactions, see:
The preferred formation of cis-isomers of 7 and 8 is known:
Consistent with this observation, the hydrogen-bonding ability of TU was diminished in THF:
For discussion on hydrogen-bonding ability of thiourea catalysts, see:
Review:
For selected examples, see:
For a general discussion on [2+2] cycloaddition, see: