Mercuric Triflate·(TMU)2 Catalyzed Cyclization of a Propargylic Ketone into a Monosubstituted Furan

Delphine Ménard; Anne Vidal; Chantal Barthomeuf; Jacques Lebreton; Pascal Gosselin

doi:10.1055/s-2005-922779

LETTER

Mercuric Triflate·(TMU)₂ Catalyzed Cyclization of a Propargylic Ketone into a Monosubstituted Furan

Delphine Ménard^a, Anne Vidal^a, Chantal Barthomeuf^b, Jacques Lebreton^c, Pascal Gosselin*^a
^a Laboratoire de Synthèse Organique - UMR-CNRS 6011, Université du Maine, Avenue Olivier Messiaen, 72085 Le Mans Cedex 9, France
Fax: +33(2)43833902; e-Mail: pascal.gosselin@univ-lemans.fr;
^b Laboratoire de Pharmacognosie et Biotechnologies, UMR-INSERM U-484, Faculté de Pharmacie, Université d’Auvergne, pl. H. Dunant, 63001 Clermont-Fd Cedex, France
^c Laboratoire de Synthèse Organique - UMR-CNRS 6513, Département Chimie, Université de Nantes, 2 rue de la Houssinière, BP 92208, 44322 Nantes Cedex 3, France

Abstract

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Abstract

Formation of a furan derivative was observed in the course of a synthetic approach towards a new carotenoid metabolite, starting from a propargylic ketone, in the presence of mercuric triflate-tetramethylurea complex.

Key words

alkynes - ketones - furans - catalysis - addition reactions

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Referenzen

References and Notes

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The red form of mercuric oxide was used although Nishizawa et al. (see ref. 11) described the reaction with the yellow form.

Typical Experimental Procedure for the Synthesis of Aldehydes 4 and 5 and Furan 11.
Tf₂O (8 µL, 0.046 mmol, 0.11 equiv) and TMU (11 µL, 0.092 mmol, 0.22 equiv) were added in succession at r.t. to a stirred suspension of mercuric oxide (red, 10 mg, 0.046 mmol, 0.11 equiv) in dry MeCN (1 mL). After 10 min, a solution of homopropargylic alcohol 3 (132 mg, 0.41 mmol, 1 equiv) in dry CH₂Cl₂ (0.5 mL) was added, immediately followed by H₂O (22 µL, 1.22 mmol, 3 equiv) and the mixture was stirred 24 h at r.t. After addition of a 1:1 mixture of sat. aq NaHCO₃ and brine (2 mL), the mixture was extracted with EtOAc (4 × 10 mL). The combined organic phases were washed with a 10% HCl solution (10 mL), dried over anhyd Na₂SO₄ and the solvent was evaporated. Purification by flash chromatography (elution with cyclohexane-EtOAc, 9:1 to 6:4) afforded OTBS-protected aldehydes (13 mg, 10%, partly separated) and unprotected aldehydes 4 and 5 (28 mg, 33%, partly separated), as colorless oils.
Analytical data for aldehyde 4 (ca. 1:2 Z:E mixture): R _f = 0.40 (eluent: cyclohexane-EtOAc, 6:4). IR (film): 3407, 2953, 2922, 2858, 1667,1458, 1364, 1190, 1117, 1048, 909, 877, 834 cm^-1. ¹H NMR (400 MHz, CDCl₃): δ = 1.00 and 1.03 [2 s, 6 H, (Me)₂-C, 1:3], 1.02 and 1.05 [2 s, 6 H, (Me)₂-C, 2:3], 1.26 (br s, 1 H, OH), 1.35 (m, 1 H), 1.78 (m, 2 H), 1.91 (br s, 3 H, Me-C=, 1:3), 2.11 (br s, 3 H, Me-C=, 2:3), 2.19 (m, 1 H), 2.82 (br s, 2 H, CH ₂CH=, 2:3), 3.21 (br s, 2 H, CH ₂CH=, 1:3), 3.98 (m, 1 H, CHOH), 5.26 (br s, 1 H, CH₂CH=), 5.88 (d, J = 8.1 Hz, 1 H, CH-CHO, 2:3), 5.99 (d, J = 8.1 Hz, 1 H, CHCHO, 1:3), 9.95 (d, J = 8.1 Hz, 1 H, CHO, 1:3), 9.99 (d, J = 8.1 Hz, 1 H, CHO, 2:3). ¹³C NMR (100 MHz, CDCl₃): δ = 17.2 (q), 24.8 (q), 29.5 (q), 29.6 (q), 29.8 (q), 31.27 (q), 31.31 (q), 34.4 (s), 34.5 (s), 37.7 (t), 37.9 (t), 40.2 (t), 46.0 (t), 48.6 (t), 65.99 (d), 66.03 (d), 128.2 (s), 128.6 (d), 128.7 (s), 129.8 (d), 135.2 (d), 136.1 (d), 161.5, 161.8 (s), 190.9 (d), 191.4 (d). GCMS (EI, 70 eV, minor diastereomer): m/z (%) = 208 (5), 190 (38), 175 (79), 157 (64), 137 (84), 119 (56), 105 (80), 91 (85), 77 (55), 43 (50), 41 (90), 39 (100). GCMS (EI, 70 eV, major diastereomer): m/z (%) = 208 (2), 175 (36), 157 (37), 147 (69), 119 (45), 107(100), 105(68), 91 (46), 79 (33), 55 (49), 41 (64), 39 (68). GCMS (CI+, i-C₄H₁₀, both diastereomers): m/z = 209 [MH⁺], 191, 173, 163, 147, 109, 95, 69. HRMS (EI): m/z calcd for C₁₃H₂₀O₂: 208.1463; found: 208.1454. Analytical data for OTBS-protected aldehyde 5: R _f = 0.52 (eluent: PE-Et₂O, 9:1). IR (film): 2955, 2928, 2857, 1727, 1643, 1471, 1381, 1360, 1256, 1080, 836, 775, 666 cm^-1. ¹H NMR (400 MHz, CDCl₃): δ = 0.06 [s, 6 H (Me)₂-Si], 0.88 (s, 9 H, t-Bu-Si), 0.97 and 0.99 [2 s, 2 × 3H, (Me)₂-C], 1.34 and 1.62 [2 m, 2 H, CH ₂-C(Me)₂], 1.79 and 2.04 (2 m, 2 H, CH ₂C=CH₂), 2.68 (br s, 2 H, CH ₂CH=C), 3.01 (br s, 2 H, CH ₂CH=O), 3.90 (dddd, J = 11.3, 9.1, 5.5, 3.6 Hz, 1 H, CHOSi), 4.95 (br s, 1 H, CH ₂=C), 5.06 (br s, 1 H, =CHCH₂), 5.15 (br s, 1 H, CH ₂=C), 9.59 (t, J = 2.5 Hz, 1 H, CHO). ¹³C NMR (100 MHz, CDCl₃): δ = -4.6 (q), 18.2 (s), 26.0 (q), 29.5 (q), 31.2 (q), 34.2 (s), 38.0 (t), 45.5 (t), 46.4 (t), 49.9 (t), 66.8 (d), 116.6 (t), 129.4 (s), 134.9 (d), 138.7 (s), 199.9 (d). HRMS (ESI): m/z calcd for C₁₉H₃₄O₂NaSi: 345.2226. Found: 345.2221.

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Depending on reaction time, small amounts of TBS-protected alcohols 4 and 5 were also isolated.

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The result is the same when the crude propargylic ketone 9 or the purified allene 10 is used for the hydration reaction.

Analytical data for 11 (ca. 3:2 mixture of cis:trans diastereoisomers): R _f = 0.34 (eluent: PE-Et₂O, 6:4). IR (film): 3352, 2954, 2926, 2866, 1715, 1647, 1588, 1501, 1461, 1364, 1258, 1149, 1044, 1015, 899, 799, 730, 597 cm^-1. ¹H NMR (400 MHz, CDCl₃): δ = 0.80, 0.86, 0.98, 0.99 (4 × s, 3 H, Me), 1.42 [br t, J = 12.5 Hz, 1 H, CH ₂C(Me)₂, 2:5], 1.61 [ddt, J = 12.7, 4.7, 1.3 Hz, 1 H, CH ₂C(Me)₂, 3:5], 1.75 (br s, 1 H, OH), 1.80 [br t, J = 12.7 Hz, 1 H, CH ₂C(Me)₂, 3:5], 1.87 [ddd, J = 12.5, 4.4, 2.1 Hz, 1 H, CH ₂C(Me)₂, 2:5], 2.07 (br t, J = 12.0 Hz, 1 H, CH ₂C=CH₂, 2:5), 2.46 (br t, J = 12.7 Hz, 1 H, CH ₂C=CH₂, 3:5), 2.57 (dd, J = 12.7, 4.5 Hz, 1 H, CH ₂C=CH₂, 3:5), 2.75 (ddd, J = 12.0, 4.9, 2.2 Hz, 1 H, CH ₂C=CH₂, 2:5), 3.14 [s, 1 H, CHC(Me₂), 3:5], 3.23 [s, 1 H, CHC(Me₂), 2:5], 3.91 (m, 1 H, CHOH), 4.58 and 4.90 (2 × br s, 2 H, CH ₂=C, 2:5), 4.83 and 4.86 (2 × br s, 2 H, CH ₂=C, 3:5), 6.06 (d, J = 3.1 Hz, 1 H, CH=CO, 3:5), 6.08 (d, J = 3.1 Hz, 1 H, CH=CO, 2:5), 6.26 (dd, J = 3.1, 1.8 Hz, 1 H, CH=CHO, 3:5), 6.32 (dd, J = 3.1, 1.8 Hz, 1 H, CH=CHO, 2:5), 7.29 (d, J = 1.8 Hz, 1 H, =CHO, 3:5), 7.34 (d, J = 1.8 Hz, 1 H, =CHO, 2:5). ¹³C NMR (100 MHz, CDCl₃): δ = 22.5, 28.1, 28.7, 30.3 (4 q, Me), 35.5 [s, C(Me)₂, major], 36.1 [s, C(Me)₂, minor], 41.8 (t, CH₂C=, major), 44.4 [t, CH₂C(Me)₂, major], 45.5 (t, CH₂C=, minor), 50.7 [t, CH₂C(Me)₂, minor], 53.6 [2 d, CHC(Me)₂], 67.6 (d, CHO, minor), 67.9 (d, CHO, major), 106.4 (d, CH=CO, major), 108.2 (d, CH=CO, minor), 109.9 (2 d, CH=CHO), 111.9 (t, CH₂=C, minor), 113.0 (t, CH₂=C, major), 140.7 (d, =CHO, major), 140.9 (d, =CHO, minor), 144.4 and 145.0 (2 s, C=CH₂), 154.0 (s, =CO, minor), 156.3 (s, =CO, major). GCMS (EI, 70 eV, cis-diastereomer, major): m/z (%) = 206 (18), 188 (66), 173 (36), 145 (26), 122 (35), 121 (100), 107 (22), 93 (34), 91 (34), 77 (28), 41 (36), 39 (39). GCMS (EI, 70 eV, trans-diastereomer, minor): m/z (%) = 206 (57), 188 (38), 173 (67), 145 (33), 122 (33), 121 (100), 107 (23), 93 (37), 91 (39), 77 (33), 41 (42), 39 (47). GCMS (CI+, MeCN): m/z = 207 [MH⁺], 189, 161, 139, 121, 95, 65. HRMS (EI): m/z calcd for C₁₃H₁₈O₂: 206.1307. Found: 206.1313.

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