TIPSOTf-Promoted Tandem Reaction through Rearrangement of Epoxides into Aldehydes with Selective Alkyl Migration Followed by Prins-Type Cyclization to Cyclopentanes

Abstract

The tandem reaction of trisubstituted epoxides to cyclopentanes promoted by TIPSOTf in nitromethane has been found. It consists of stereospecific rearrangement of epoxides into aldehydes accompanied with selective alkyl migration and subsequent Prins-type cyclization of the aldehydes generated to cyclopentanes.

Key words

cyclization - epoxides - rearrangement - steric hindrance - tandem reaction

References and Notes

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• 12a The optical purities of 15 and 19 were determined to be 84% ee and 74% ee by derivatization of epoxy alcohols, which were prepared from geraniol and nerol by Sharpless asymmetric epoxidation using diethyl l-(+)-tartrate (ref. 5), to their (R)-α-methoxy-α-trifluoromethylphenylacetyl (MTPA) esters and integration of the ^¹H NMR and ^¹9F NMR spectra, respectively: Dale JA. Dull DL. Mosher HS. J. Org. Chem.  1969,  34:  2543 
• 12b

  The optical purities of 16a, 16b, and ent-16a were determined to be 84% ee, 84% ee, and 74%ee, respectively, by derivatization of desilylated diols in 16a, 16b, and ent-16a to their di(R)-MTPA esters and integration of the ^¹H NMR (16a and 16b) and ^¹9F NMR (ent-16a) spectra.

• 13 Jung ME. Anderson KL. Tetrahedron Lett.  1997,  38:  2605 

9

Typical Procedure for the Tandem Reaction: To a solution of epoxide 7b (R^¹ = TMS, 30.0 mg, 0.100 mmol), prepared from 7a (R^¹ = H, ref. 8) according to footnote d in Table  [¹] , in nitromethane (1.0 mL) were successively added dropwise 2,6-lutidine (92 µL, 0.703 mmol) and triisopropyl-silyl triflate (0.135 mL, 0.502 mmol) under a nitrogen atmosphere at 0 ˚C, and the mixture was stirred at the same temperature for 45 min. H₂O was added to the solution, and the aqueous layer was extracted with hexane. The organic layer was washed with brine, dried over anhyd Na₂SO₄, and concentrated under reduced pressure. The residue was purified by flash column chromatography (hexane-benzene, 98:2) on silica gel to afford a mixture of cyclopentanes 12a and 12b (29.4 mg, 64% yield) in a ratio of 3.2:1 as a colorless oil; R _f 0.58 (hexane-benzene, 95:5). ^¹H NMR (400 MHz, CDCl₃): δ = 4.77 (s, 1 H), 4.71 (s, 1 H), 3.88 (d, J = 6.6 Hz, 0.24 H), 3.82 (d, J = 7.3 Hz, 0.76 H), 2.53-2.64 (m, 1 H), 1.14-1.93 (m, 8 H), 1.72 (s, 3 H), 1.22 (s, 1.44 H), 1.20 (s, 4.56 H), 0.97-1.12 (m, 21 H), 0.94 (s, 0.72 H), 0.90 (s, 2.28 H), 0.10 (s, 9 H). ^¹³C NMR (75 MHz, CDCl₃): δ = 147.3, 147.2, 111.1, 110.7, 84.1, 77.2, 74.0, 54.8, 53.7, 45.6, 45.4, 39.9, 39.4, 35.3, 34.8, 34.2, 29.8, 26.7, 24.1, 20.0, 19.7, 18.6, 18.5, 18.4, 13.4, 13.3, 2.7, 2.6. IR (neat): 3076, 1641, 1462, 1378, 1107, 882 cm^-¹. HRMS (FAB): m/z [M - H⁺] calcd for C₂₆H₅₃O₂Si₂: 453.3584; found: 453.3591.

11

Compound 16a: R _f = 0.62 (hexane). ^¹H NMR (400 MHz, CDCl₃): δ = 4.77-4.81 (m, 1 H), 4.68-4.72 (m, 1 H), 4.24 (d, J = 7.3 Hz, 1 H), 3.44 (d, J = 9.5 Hz, 1 H), 3.30 (d, J = 9.8 Hz, 1 H), 2.59 (dt, J = 9.9, 7.1 Hz, 1 H), 1.82-1.93 (m, 1 H), 1.74 (dt, J = 12.2, 8.4 Hz, 1 H), 1.72 (s, 3 H), 1.32-1.42 (m, 1 H), 1.27 (ddd, J = 12.4, 7.9, 4.6 Hz, 1 H), 1.00-1.09 (m, 21 H), 0.90 (s, 9 H), 0.88 (s, 3 H), 0.03 (s, 3 H), 0.02 (s, 3 H). ^¹³C NMR (75 MHz, CDCl₃): δ = 147.3, 111.0, 77.3, 67.6, 54.2, 48.0, 32.6, 26.8, 25.9, 19.6, 18.4, 18.3, 17.9, 13.3, -5.5, -5.6. IR (neat): 3079, 1644, 1463, 1254, 1087, 835 cm^-¹. HRMS (FAB): m/z [M⁺] calcd for C₂₅H₅₂O₂Si₂: 440.3506; found: 440.3515.
Compound 16b: R _f 0.51 (hexane). ^¹H NMR (400 MHz, CDCl₃): δ = 4.74-4.78 (m, 1 H), 4.70-4.74 (m, 1 H), 3.97 (d, J = 7.1 Hz, 1 H), 3.63 (d, J = 10.0 Hz, 1 H), 3.50 (d, J = 10.0 Hz, 1 H), 2.63 (dt, J = 9.3, 7.0 Hz, 1 H), 1.81-1.94 (m, 2 H), 1.72 (s, 3 H), 1.32-1.44 (m, 1 H), 1.18-1.31 (m, 1 H), 0.97-1.10 (m, 21 H), 1.02 (s, 3 H), 0.90 (s, 9 H), 0.04 (s, 3 H), 0.03 (s, 3 H). ^¹³C NMR (75 MHz, CDCl₃): δ = 147.2, 110.9, 83.9, 66.5, 55.3, 48.0, 33.1, 27.3, 26.0, 22.9, 19.9, 18.39, 18.37, 18.32, 13.2, -5.45, -5.49. IR (neat): 3079, 1642, 1463, 1086, 835 cm^-¹. HRMS (FAB): m/z [M - H⁺] calcd for C₂₅H₅₁O₂Si₂: 439.3427; found: 439.3422.