Formation of 1-Ethenylcyclopropanols Involving Kulinkovich Cyclo­propanation and Peterson Olefination of α-Trimethylsilylesters

Abstract

Mercuric iodide catalyzed condensation of bis-silyl­ketene acetals with benzaldehyde provided a 1:1 erythro and threo mixture of α-trimethylsilylesters. Only the threo adducts underwent titanium(IV)-mediated cyclopropanation and acid induced Peterson olefination to provide (Z)-1-ethenylcyclopropanols of considerable synthetic potential.

Key words

condensation - elimination - ring closure - titanium - neighbouring group effect

References

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• 18c

  However, there are no intramolecular hydrogen bond in the O-silylated diastereoisomers 6a,b and 7a,b. The coupling constants of erythro- 6a [J(H₂H₃) = 10.7 Hz] and of threo -7a [J(H₂H₃) = 10.4 Hz] were carefully measured by peak pickings.

• 19 Colvin EW. In Silicon Reagents in Organic Synthesis   Academic Press; London/New York: 1988.  p.101 
• To a solution of 4 g (11 mmol) of the 1:1 mixture of ethyl 3-phenyl-2-(trimethylsilyl)-3-(trimethylsilyloxy)propionate erythro -6a and threo- 7a in 15 mL of THF containing 0.62 g (2.2 mmol; 0.2 equiv) of Ti(i-PrO)₄ was added dropwise a 2.54 M solution of ethylmagnesium bromide (11 mL, 27 mmmol; 2.5 equiv) in diethyl ether within 4 h. The reacting mixture was cooled to 0 °C (iced-water bath), then diluted with diethyl ether and hydrolyzed with 10 mL of aq NH₄Cl. After filtration through celite, the separated organic layer was washed with brine, dried on Na₂SO₄ and concentrated in vacuo. Flash chromatography of the residue (eluant: pentane/diethyl ether 9:1) gave two products:
• 20a

  1-[2-Phenyl-1-(trimethylsilyl)-2-(trimethylsilyl-oxy)ethyl]cyclopropanol 9a: 1.94 g (52% yield); ¹H NMR (250 MHz, CDCl₃) δ -0.08 (s, 9 H), 0.71 (d, J = 4.95 Hz, 1 H), 0.25-0.88 (m, 4 H), 3.24 (s, 1 H), 5.33 (d, J = 4.95 Hz, 1 H), 7.19-7.33 (m, 5 H); ¹³C NMR (66 MHz, CDCl₃): δ 0.21, 0.28, 13.27, 15.62, 46.13, 58.92, 78.75, 126, 126.9, 127.9, 144.4; IR 3463, 3379, 2974, 2949 cm^-1; MS m/z (EI) 322 (2) [M⁺], 231 (42), 179 (31), 147 (17), 75 (36), 73 (100), 45 (16); MS m/z (CI with NH₃) 340 (0.1), 252 (17), 251 (61), 250 (100), 233 (40), 232 (44), 231 (74) 217 (18), 179 (21), 160 (21), 155 (15), 144 (26), 1433 (100).
  

• 20b

  1-(2-Hydroxy-2-phenyl-1-trimethylsilylethyl)cyclo-propanol 9a′: (various amounts 5-10%); white solid: mp 107 °C; ¹H NMR (250 MHz, CDCl₃) δ -0.07 (s, 9 H), 0.76 (s, 1 H), 0.07-0.97 (m, 4 H), 2.58 (s, 1 H), 3.29 (s, 1 H), 5.44 (s, 1 H), 7.24-7.35 (m, 5 H); ¹³C NMR (66 MHz, CDCl₃) δ 0.32, 13.41, 16.02, 44.86, 59.97, 77.97, 125.17, 126.91, 128.09, 144.41; IR: 3468, 2955, 2898 cm^-1; MS m/z (EI) 231 (33), 159 (33), 145 (16), 131 (33), 115 (12), 103 (16), 79 (27), 77 (44), 75 (93), 73 (100), 79 (27), 45 (26); MS m/z (CI with NH₃) 251 (19), 250 (81) [M⁺], 231 (10), 161 (16), 160 (13), 144 (13), 143 (100) 131 (8); Exact mass M⁺ 250.1377 (calcd for C₁₄H₂₂SiO₂ 250.1389).

• 23 Salaün J. Ollivier J. Nouv. J. Chem.  1981,  5:  587 
• 24 Ollivier J. PhD Thesis   Université de Paris-Sud; Orsay France: 1986. 
• 25 Colvin EW. In Silicon Reagents in Organic Synthesis   Academic Press; New York: 1988.  p.65-69  
• 27 Molecular mechanics calculations (using a MM⁺ force field) and semi-empirical ZINDO calculations have been performed with the Hyperchem software (version 5.1). The Ti-O and Ti-C bond lengths and the Ti-bond angles were in accord with reported RX data for titanium complexes. See: Gais HJ. Volhardt J. Linder HJ. Paulus H. Angew. Chem., Int. Ed. Engl.  1988,  27:  1541 

21

Base-induced Peterson olefination of cyclopropanols 9a and 11a led to ring-opened derivatives (see ref. 1).

22

To a stirred solution of 340 mg (1 mmol) of cyclopropanol 9a in 5 mL of methanol at r.t. was added two drops of chlorotrimethylsilane. The reaction was complete within 2 h, as monitored by TLC. Then the solvent was removed in vacuo; flash chromatography of the residue (eluant: pentane/diethyl ether 9:1) gave 128 mg (76% yield) of 1-(Z)-styryl cyclopropanol 12. ¹H NMR (250 MHz, CDCl₃) δ 0.71-1.32 (m, 4 H), 2.16 (s, 1 H), 5.26 (d, J = 13 Hz, 1 H), 6.53 (d, J = 13 Hz, 1 H), 7.32-7.55 (m, 5 H); MS m/z (EI) 160 (41) [M⁺], 159 (74), 145 (54), 131 (68), 127 (36), 115 (43), 103 (63), 91 (33), 77 (100), 51 (52); MS m/z (CI with NH₃) 178 (100), 161 (22), 160 (17), 159 (14), 143 (18), 131 (13).

26

X-ray crystallographic data of the diol 9a′, will be published in Zeitschrift fuer Kristallographie.