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.

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

References

1a Salaün J. In The Chemistry of the Cyclopropyl Group, Rearrangements Involving the Cyclopropyl Group   Rappoport Z. Wiley; New York: 1987.  p.809-878  

1b Salaün J. Top. Curr. Chem.  1988,  144:  1 ; and references cited therein

1c Carbocyclic Three- and Four-membered Ring systems In, Houben-Weyl Methods of Organic Chemistry   Vol. E 17a-f:  de Meijere A. Thieme; Stuttgart: 1997. and references cited therein

2a Schnaubelt J. Ullmann A. Reissig H.-U. Synlett  1995,  1223 

2b Ulmann A. Reissig H.-U. Rademacher O. Eur. J. Org. Chem.  1998,  2541 

2c Palia PK. Reissig H.-U. Synlett  2001,  33 

3a Stolle A. Ollivier J. Piras PP. Salaün J. de Meijere A. J. Am. Chem. Soc.  1992,  114:  4051 

3b Ollivier J. Dorizon P. Piras PP. de Meijere A. Salaün J. Inorg. Chim. Acta  1994,  222:  37 

3c Salaün J. Russian J. Org. Chem.  1997,  33:  742 

4a Ollivier J. Girard N. Salaün J. Synlett  1999,  1539 

4b Paschetta V. Cordero FM. Paugam R. Ollivier J. Salaün J. Synlett  2001,  1233 

5a Chevtchouk T. Ollivier J. Salaün J. Tetrahedron: Asymmetry  1997,  8:  1005 

5b Chevtchouk T. Ollivier J. Salaün J. Tetrahedron : Asymmetry  1997,  8:  1011 

5c Stolle A. Becker H. Salaün J. de Meijere A. Tetrahedron Lett.  1994,  35:  3517 

5d Stolle A. Becker H. Salaün J. de Meijere A. Tetrahedron Lett.  1994,  35:  3521 

5e Atlan V. Racouchot S. Rubin M. Bremer C. Ollivier J. de Meijere A. Salaün J. Tetrahedron: Asymmetry  1998,  9:  1131 

5f Estieu K. Paugam R. Ollivier J. Salaün J. Cordero FM. Goti A. Brandi A. J. Org. Chem.  1997,  62:  8276 

5g Ferrara M. Cordero FM. Goti A. Brandi A. Estieu K. Paugam R. Ollivier J. Salaün J. Eur. J. Org. Chem.  1999,  2725 

5h Pisaneschi F. Cordero FM. Goti A. Paugam R. Ollivier J. Brandi A. Salaün J. Tetrahedron: Asymmetry  2000,  11:  897 

5i Cordero FM. Pisaneschi F. Goti A. Ollivier J. Salaün J. Brandi A. J. Am. Chem. Soc.  2000,  122:  8075 

5j Delogu G. Salaün J. de Candia C. Fabbri D. Piras PP. Ollivier J. Synthesis  2002,  2271 

6 Salaün J. Conia JM. Tetrahedron Lett.  1972,  2849 

7 Denis JM. Girard C. Conia JM. Synthesis  1972,  549 

8 Salaün J. Chem. Rev.  1983,  83:  619 

9 Salaün J. Chem. Rev.  1989,  89:  1247 

10a Kulinkovich OG. Sviridov SV. Vasilevskii DA. Pritcyckaja JS. Zh. Org. Khim.  1989,  25:  2245 

10b Kulinkovich OG. Sviridov SV. Vasilevskii DA. Synthesis  1991,  234 

10c Kulinkovich OG. Sviridov SV. Vasilevskii DA. Savchenko AI. Pritytskaya TS. Zh. Org. Khim.  1991,  27:  294 

10d Kulinkovich OG. de Meijere A. Chem. Rev.  2000,  100:  2789 ; and references cited therein

10e Kulinkovich OG. Pure Appl. Chem.  2000,  72:  1715 ; and references cited therein

11 Kozyrkov Y. Pukin A. Kulinkovich OG. Ollivier J. Salaün J. Tetrahedron Lett.  2000,  41:  6399 

12 Sylvestre I. Ollivier J. Salaün J. Tetrahedron Lett.  2001,  42:  4991 

13a Racouchot S. Ollivier J. Salaün J. Synlett  2000,  1729 

13b Racouchot S. Sylvestre I. Ollivier J. Kozyrkov Y.-Y. Pukin A. Kulinkovich OG. Salaün J. Eur. J. Org. Chem.  2002,  2160 

14 Chan TH. Acc. Chem. Res.  1977,  10:  442 

15 Brandi A. Goti A. Chem. Rev.  1998,  98:  589 

16 Fleming I. Dunoges J. Smithers R. Org. React.  1989,  37:  57 

17 The cyclopropanol 2a (R¹ = H) was previously isolated as 3,5-dinitrobenzoate from the alkylation-cyclization of ethyl 3-bromopropionate by Me₃SiCH₂MgBr/SmI₂, see: Fukuzawa S. Furuya H. Tsuchimoto T. Tetrahedron  1996,  52:  1953 

18a Dicker IB. J. Org. Chem.  1993,  51:  2324 

18b In this article (ref.) the J(threo) > J(erythro) relationship for the H₂H₃ coupling constants, was erroneously based on the consideration of stronger intramolecular hydrogen bonds in the threo comparatively to the erythro adducts, see: House HO. Crumrine DS. Teranishi AY. Olmstead HD. J. Am. Chem. Soc.  1973,  95:  3310 

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).

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).

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  

26

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

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