Asymmetric Synthesis of Dihydrofurans via Rh(II)-Catalyzed Cyclopropanation-Rearrangement of Enol Ethers with 1-(Silanyloxy)vinyl Diazoacetates

Paul Müller; Gérald Bernardinelli; Yves F. Allenbach; Maria Ferri; Stéphane Grass

doi:10.1055/s-2005-868501

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Synlett 2005(9): 1397-1400
DOI: 10.1055/s-2005-868501

LETTER

Asymmetric Synthesis of Dihydrofurans via Rh(II)-Catalyzed Cyclopropanation-Rearrangement of Enol Ethers with 1-(Silanyloxy)vinyl Diazoacetates

Paul Müller*, Gérald Bernardinelli, Yves F. Allenbach, Maria Ferri, Stéphane Grass
Department of Organic Chemistry, University of Geneva, 30, Quai Ernest Ansermet, 1211 Geneva 4, Switzerland
Fax: +41(22)3793215; e-Mail: paul.muller@chiorg.unige.ch;

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Publication History

Received 14 February 2005
Publication Date:
29 April 2005 (online)

Abstract
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Abstract

The cyclopropanation of dihydrofuran and dihydropyran with methyl 1-(silanyloxy)vinyl diazoacetates in the presence of chiral Rh(II)-catalysts affords cyclopropanes with high diastereo- and enantioselectivitiy. The cyclopropanes, in turn, rearrange to dihydrofurans upon desilylation with TBAF.

Key words

carbenes - catalysis - diazo compounds - transition metals - stereoselectivity

References

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10

Data of Methyl (1 R ^* ,5 S ^* ,6 S ^* )-6-{1-[( tert -Butyldi-methyl)silanyloxy]vinyl}-2-oxabicyclo[3.1.0]hexane-6-carboxylate ( 5a). [α]_D ¹⁸ -19 (c 1.12, EtOH, for 64% ee). IR (film): 2952 (w), 2855 (w), 1715 (s), 1632 (m), 1251 (s). ¹H NMR (500 MHz, CDCl₃): δ = 0.21 (d, J = 1.6 Hz, 6 H), 0.92 (s, 9 H), 2.14-2.19 (m, 1 H), 2.22-2.30 (m, 1 H), 2.41 (t, J = 6.0 Hz, 1 H), 3.65 (s, 3 H), 3.80 (dd, J = 8.5, 17.5 Hz, 1 H), 4.09 (ddd, J = 8.5, 10.1, 17.5 Hz, 1 H), 4.23 (d, J = 5.7 Hz, 1 H). ¹³C NMR (125 MHz, CDCl₃): δ = -5.3 (q), -4.7 (q), 18.0 (s), 25.5 (q), 26.0 (t), 32.4 (d), 39.5 (s), 51.9 (q), 70.7 (d), 71.8 (t), 96.0 (t), 150.5 (s), 171.2 (s). MS: m/z (%) = 298 (7)[M⁺], 242 (23), 241 (100), 209 (12), 166 (12), 89 (58), 75 (36), 73 (78), 59 (30). HRMS: m/z calcd for C₁₅H₂₆O₄Si⁺: 298.1601; found: 298.1642.

11

Data of Methyl (1 R ^* ,5 S ^* ,6 S ^* )-6-{1-[Tri(isopropyl)silanyl-oxy]vinyl}-2-oxabicyclo[3.1.0]hexane-6-carboxylate ( 5b).
[α]_D ²⁰ -8 (c 1.09, CHCl₃, for 82% ee). IR (film): 2946 (m), 2895 (w), 2867 (m), 1716 (s), 1631 (m), 1464 (m), 1331 (s), 1256 (s), 1181 (m), 1133 (m), 1113 (w). ¹H NMR (500 MHz, CDCl₃): δ = 1.10 (d, J = 7.3 Hz, 9 H), 1.11 (d, J = 7.4 Hz, 9 H), 1.25 (sept, J = 7.4 Hz, 3 H), 2.18-2.31 (m, 2 H), 2.43 (br t, J = 5.8 Hz, 1 H), 3.64 (s, 3 H), 3.85 (dd, J = 8.4, 17.1 Hz, 1 H), 4.10 (ddd, J = 8.4, 10.3, 17.1 Hz, 1 H), 4.22 (d, J = 5.7 Hz, 1 H), 4.36 (d, J = 1.0 Hz, 1 H), 4.39 (d, J = 1.0 Hz, 1 H). ¹³C NMR (125 MHz, CDCl₃): δ = 12.7 (d), 17.9 (q), 18.0 (q), 26.0 (t), 32.4 (d), 39.8 (s), 51.8 (s), 70.8 (d), 71.9 (t), 95.3 (t), 150.6 (s), 171.3 (s). MS: m/z (%) = 340 (4)[M⁺], 297 (100), 117 (14), 115 (12), 89 (21), 87 (13), 77 (10), 75 (34), 73 (18), 61 (13), 59 (38). HRMS: m/z calcd for C₁₈H₃₂O₄Si⁺: 340.2070; found: 340.2062.

14

Data of Methyl cis -2-Methyl-3a,4,5,6a-tetrahydro-furo[2,3- b ]furan-3-carboxylate ( 3).
[α]_D ¹⁸ +147 (c 1.12, EtOH, for 64% ee); [α]_D ¹⁸ +223 (c 1.13, for 84% ee). IR (film): 2952 (w), 1653 (s), 1641 (s), 1230 (s), 1080 (s). ¹H NMR (300 MHz, CDCl₃): δ = 2.06-2.13 (m, 2 H), 2.26 (d, J = 1.4 Hz, 3 H), 3.67-3.76 (m, 1 H), 3.76 (s, 3 H), 4.05-4.11 (m, 1 H), 6.12 (d, J = 6.2 Hz, 1 H). ¹³C NMR (125 MHz, CDCl₃): δ = 14.2 (q), 31.7 (t), 47.0 (d), 50.9 (d), 67.1 (t), 103.4 (s), 109.7 (d), 165.9 (s). MS: m/z (%) = 184 (31)[M⁺], 153 (30), 152 (100), 125 (14), 124 (16), 110 (41), 109(16), 96 (17), 95 (15), 82 (29), 81 (14), 53 (18). HRMS: m/z calcd for C₉H₁₂O₄ ⁺: 184.0736; found: 184.0731. Enantiomer separation: GC (β-Dex, isothermal, 120 °C, τ₁ = 20.1 min, τ₂ = 22.0 min or β-Dex, isothermal, 130 °C, τ₁ = 12.6 min, τ₂ = 13.7 min). For data of ethyl ester corresponding to 3, see ref. [15]

16

Data of Methyl (1 R ^* ,6 S ^* ,7 S ^* )-7-{1-[Tri(isopropyl)silanyl-oxy]vinyl}-2-oxabicyclo[4.1.0]heptane-7-carboxylate ( 9). Colorless oil. [α]_D ²⁰ -22 (c 1.07, CHCl₃, for 84% ee), [α]_D ²⁰ -32 (c 0.56, Et₂O, for 95% ee). IR (film): 2945 (m), 2866 (m), 1717 (s), 1633 (m), 1464 (m), 1390 (w), 1335 (m), 1282 (w), 1254 (s), 1237 (s), 1219 (m), 1204 (m), 1159 (m), 1133 (m), 1076 (s), 1042 (m), 1020 (s), 912 (w), 881 (m), 745 (s), 680 (s). ¹H NMR (500 MHz, CDCl₃): δ = 0.95-1.09 (m, 1 H), 1.22 (d, J = 6.6 Hz, 9 H), 1.23 (d, J = 6.6 Hz, 9 H), 1.24-1.31 (m, 3 H), 1.59-1.73 (m, 2 H), 1.96-1.99 (m, 1 H), 2.02-2.06 (m, 1 H), 3.11-3.17 (m, 1 H), 3.41 (s, 3 H), 3.51-3.56 (m, 1 H), 4.15 (d, J = 7.4 Hz, 1 H), 4.56 (d, J = 0.7 Hz, 1 H), 4.64 (d, J = 0.7 Hz, 1 H). ¹³C NMR (125 MHz, CDCl₃): δ = 13.1 (d), 17.1 (t), 18.2 (q), 18.3 (q), 22.1 (t), 24.9 (d), 36.8 (s), 51.4 (q), 62.2 (d), 64.3 (t), 96.5 (d), 151.6 (s), 172.4 (s). MS: m/z (%) = 354 (2)[M⁺], 312 (23), 311 (100), 117 (10), 89 (15), 75 (23), 73 (10), 59 (26). HRMS: m/z calcd for C₁₉H₃₄O₄Si⁺: 354.2226; found: 354.2181.

17

Data of Methyl cis -6-Tri(isopropyl)silanyloxy-2,3,4,4a,7,7a-hexahydrocyclopenta[ b ]pyran-5-carboxylate ( 10).
IR (film): 2944 (m), 2866 (m), 1716 (w), 1693 (s), 1614 (s), 1463 (w), 1437 (m), 1383 (s), 1287 (w), 1233 (s), 1212 (s), 1188 (m), 1141 (m), 1105 (m), 1082 (s), 1050 (m), 1009 (w), 996 (w), 881 (s), 843 (w), 807 (s), 781 (s), 682 (s). ¹H NMR (500 MHz, CDCl₃): δ = 1.10 (d, J = 7.3 Hz,¹ 9 H), 1.11 (d, J = 7.5 Hz, 9 H), 1.17-1.25 (m, 3 H), 1.39-1.47 (m, 1 H), 1.54-1.62 (m, 1 H), 1.86-1.98 (m, 2 H), 2.53 (dd, J = 0.6, 5.5 Hz, 2 H), 2.85 (dd, J =12.1, 6.0 Hz, 1 H), 3.49-3.54 (m, 1 H), 3.66-3.73 (m, 1 H), 3.69 (s, 3 H), 4.15 (dd, J = 11.0, 5.5 Hz, 1 H). ¹³C NMR (125 MHz, CDCl₃): δ = 12.9 (d), 17.7 (q), 17.8 (q), 22.2 (t), 24.0 (t), 40.4 (d), 40.6 (t), 50.4 (q), 64.4 (t), 72.9 (d), 109.4 (s), 163.9 (s), 165.5 (s). MS: m/z (%) = 354 (1)[M⁺], 312 (22), 311 (100), 89 (10), 75 (14), 59 (18). HRMS: m/z calcd for C₁₉H₃₄O₄Si⁺:354.2226; found: 354.2255.

20

Crystal data for (C₂₅H₃₆N₂O₈Si), rac-13: M = 520.7, triclinic, P, a = 10.0195 (7), b = 13.3063 (8), c = 21.6204 (14)Å, α = 81.287 (7), β = 85.175 (8), γ = 75.576 (7)°, U = 2756.2 (3)Å³, T = 200 K, Z = 4, µ (MoK_α) = 0.133 mm^-1 . The final R(F) = 0.047, wR(F)= 0.043 and S = 1.05. Both molecules of the asymmetric unit show similar conformations. CCDC-258850.

21

Data of Methyl cis -2-Methyl-3 a ,5,6,7 a -tetrahydro-4 H -furo[2,3- b ]pyran-3-carboxylate ( 11).
[α]_D ¹⁸ +144 (c 1.06, CHCl₃, for 95% ee). IR (film): 2950 (w), 1693 (s), 1633 (w), 1436 (m), 1381 (m), 1359 (w), 1333 (m), 1311 (w), 1259 (m), 1222 (w), 1187 (m), 1163 (m), 1139 (m), 1117 (m), 1085 (s), 1041 (w), 993 (m), 922 (m), 893 (m), 852 (s). ¹H NMR (400 MHz, CDCl₃): δ = 1.56-1.67 (m, 3 H), 1.92-1.98 (m, 1 H), 2.23 (d, J = 1.4 Hz, 3 H), 2.96-3.01 (m, 1 H), 3.70 (s, 3 H), 3.74-3.81 (m, 2 H), 5.77 (d, J = 7.6 Hz, 1 H). ¹³C NMR (100 MHz, CDCl₃): δ = 14.3 (q), 19.8 (t), 22.1 (t), 37.9 (d), 50.8 (q), 60.8 (t), 104.1 (d), 106.7 (s), 166.2 (s), 167.7 (s). MS: m/z (%) = 198 (18)[M⁺], 167 (20), 166 (100), 139 (10), 138 (15), 124 (45), 110 (14), 96 (16), 95 (16), 82 (13), 67 (11). HRMS: m/z calcd for C₁₀H₁₄O₄ ⁺: 198.0892; found: 198.0903. Enantiomer separation: GC (β-Dex, isothermal, 130 °C, τ₁ = 19.0 min, τ₂ = 19.7 min). For data of ethyl ester corresponding to 11 see ref. 1, 15, 22.