Diastereoselective Domino Heck-Suzuki
Reaction: Synthesis of Substituted Methylenetetrahydrofurans

Manfred Braun; Brigitte Richrath

doi:10.1055/s-0028-1088217

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Synlett 2009(6): 968-972
DOI: 10.1055/s-0028-1088217

LETTER

Diastereoselective Domino Heck-Suzuki Reaction: Synthesis of Substituted Methylenetetrahydrofurans

Manfred Braun*, Brigitte Richrath
Institut für Organische Chemie und Makromolekulare Chemie, Universität Düsseldorf, Universitätsstr. 1, 40225 Düsseldorf, Germany
Fax: +49(211)8115079; e-Mail: braunm@uni-duesseldorf.de;

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Publication History

Received 25 November 2008
Publication Date:
16 March 2009 (online)

Abstract
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Abstract

In a palladium-catalyzed reaction of dienyl ethers with boronic acids, a diastereoselective cyclization occurs to give methylenetetrahydrofurans. They can be obtained as pure enantiomers and their conversion into dihydro-3(2H)-furanones and dioxanones is demonstrated.

Key words

palladium - catalysis - cyclizations - stereoselectivity - chirality

References and Notes

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15

Typical Procedure for the Preparation of Compound 1aa
To a stirred solution of 3a (0.253 g, 1.00 mmol) in EtOH (10 mL) under an argon atmosphere were added PhB(OH)₂ (4a, 0.183 g, 1.50 mmol), Cs₂CO₃ (0.489 g, 1.5 mmol), Pd(OAc)₂ (5.5 mg, 0.0025 mmol), and tri-o-tolylphosphane (5.1 mg, 0.0025 mmol). After stirring for 24 h at 25 ˚C, the solvent was removed in a rotary evaporator. The residue was dissolved in a mixture of Et₂O (40 mL) and deionized H₂O (40 mL). The aqueous layer was separated and extracted with three 20 mL portions of Et₂O. The combined organic layers were dried with anhyd MgSO₄, and the solvent was evaporated under reduced pressure. The yellow-brown crude product was purified by column chromatography on SiO₂ (hexane-EtOAc, 6:1) to give yellowish, oily 1aa (0.153 g, 61%).

16

Spectroscopic Data Compound 1aa: ^¹H NMR (500 MHz, CDCl₃): δ = 2.38 (m, 2 H, CH₂Ph), 2.93 (m, 1 H, 3-H), 4.41 (dq, J _d = 13.16 Hz, J _q = 2.13 Hz, 1 H, 5-H), 4.54 (dt, J _d = 13.24 Hz, J _t = 1.66 Hz, 1 H, 5-H), 4.61 (d, J = 6.31 Hz, 1 H, 2-H), 4.75 (q, J = 2.36 Hz, 1 H, C=CHH), 4.90 (q, J = 2.05 Hz, 1 H, C=CHH), 7.19 (m, 10 H, arom. H). This cis-diastereomer differs in δ = 4.63 (d, J = 1.90 Hz, 1 H, 2-H). ^¹³C NMR (125 MHz, CDCl₃): δ = 38.7, 53.0, 71.9, 86.4, 105.5, 115.7, 121.1, 126.6, 126.7, 128.0, 128.7, 129.6, 130.1, 139.7, 141.8, 151. 3. GC-MS (t _R = 9.71 min): m/z (%) = 250 (2) [M]⁺, 158 (43), 129 (100).
Compound (2R,3R)-1aa: [α]_D ^²0 -3.1 (c 1, CHCl₃).
Compound 1ab: ^¹H NMR (500 MHz, CDCl₃): δ = 2.80 (m, 2 H, CH₂Ar), 2.89 (m, 1 H, 3-H), 4.40 (m, 1 H, 5-H), 4.53 (m, 1 H, 5-H), 4.57 (d, J = 6.31 Hz, 1 H, 2-H), 4.76 (q, J = 2.21 Hz, 1 H, C=CHH), 4.90 (q, J = 1.26 Hz, 1 H, C=CHH), 7.22 (m, 9 H, arom. H). This cis-diastereomer differs in δ = 4.61 (d, J = 1.58 Hz, 1 H, 2-H). ^¹³C NMR (125 MHz, CDCl₃): δ = 16.57, 32.94, 41.62, 71.83, 85.27, 105.52, 125.82, 126.77, 127.35, 128.73, 129.57, 130.08, 131.97, 130.06, 144.22, 152.99. GC-MS [t _R = 12.06 min(trans); t _R = 12.10 min(cis)]: m/z (%) = 296 (23) [M]⁺, 158 (50), 137 (100).
Compound 1ac: ^¹H NMR (500 MHz, CDCl₃): δ = 2.90 (m, 2 H, CH₂Ar), 2.98 (m, 1 H, 3-H), 4.50 (m, 1 H, 5-H), 4.64 (m, 1 H, 5-H), 4.65 (d, J = 6.0 Hz, 1 H, 2-H), 4.84 (d, J = 1.89 Hz, 1 H, C=CHH), 5.01 (d, J = 1.58 Hz, 1 H, C=CHH), 7.09 (d, J = 8.20 Hz, 2 H, m-ArCl), 7.28 (m, 7 H, arom. H). ^¹³C NMR (125 MHz, CDCl₃): δ = 22.02, 27.96, 31.83, 35.68, 69.25, 86.53, 101.37, 124.51, 127.04, 129.65, 130.51, 141.74, 154.69. GC-MS (t _R = 10.70 min): m/z (%) = 284 (5) [M]⁺, 158 (72), 143 (100).
Compound 1ad: ^¹H NMR (500 MHz, CDCl₃): δ = 0.81 (m, 3 H, CH₃), 1.21 (m, 10 H, CH₂), 1.87 (m, 1 H, CHCHH), 2.33 (m, CHCHH), 2.58 (m, 1 H, 3-H), 4.35 (dq, J _d = 13.24 Hz, J _q = 2.21 Hz, 1 H, 5-H), 4.54 (m, 1 H, 5-H), 4.92 (q, J = 2.05 Hz, 1 H, 2-H), 5.27 (m, 2 H, C=CHH, CH=CH), 5.41 (m, 2 H, C=CHH, CH=CH), 7.27 (d, J = 4.10 Hz, 2 H, o-arom. H), 7.38 (t, J = 7.72 Hz, 2 H, m-arom. H), 7.53 (dd, J = 1.10, 8.35 Hz, 1 H, p-arom. H). ^¹³C NMR (125 MHz, CDCl₃): δ = 15.0, 21.2, 24.4, 27.9, 31.5, 33.1, 34.7, 58.1, 70.5, 90.3, 109.6, 125.0, 126.1, 127.6, 129.2, 130.0, 136.5, 149.9. GC-MS (t _R = 10.70 min): m/z (%) = 284 (32) [M]⁺, 269 (38), 172 (45), 158 (100).
Compound 1ae: ^¹H NMR (500 MHz, CDCl₃): δ = 1.25 (d, J = 6.31 Hz, 6 H, CH₃), 1.29 (m, 2 H, CH ₂Ph), 1.38 (m, 1 H, CHCH₃), 2.94 (q, J = 7.25 Hz, 1 H, 3-H), 4.75 (m, 2 H, 5-H), 5.13 (d, J = 10.40 Hz, 1 H, 2-H), 5.27 (t, J = 1.42 Hz 1 H, C=CHH), 5.30 (t, J = 1.42 Hz, 1 H, C=CHH), 7.25 (m, 5 H, arom. H). ^¹³C NMR (125 MHz, CDCl₃): δ = 22.02, 27.96, 31.83, 35.68, 69.25, 86.53, 101.37, 124.51, 127.04, 129.65, 130.51, 141.74, 154.69. GC-MS (t _R = 10.70 min): m/z (%) = 165 (10) [M - C₄H₃]⁺, 139 (12), 123 (85), 97 (100).
Compound 1ba: ^¹H NMR (500 MHz, CDCl₃): δ = 0.93 (d, J = 6.31 Hz, 3 H, CH₃), 2.63 (m, 2 H, CH₂Ph), 2.87 (m, 1 H, 3-H), 3.68 (quint, J = 6.46 Hz, 1 H, 2-H), 4.21 (dq, J _d = 13.24 Hz, J _q = 2.21 Hz, 1 H, 5-H), 4.35 (dt, J _d = 13.24 Hz, J _t = 1.42 Hz, 1 H, 5-H), 4.79 (q, J = 2.21 Hz, 1 H, C=CHH), 4.78 (q, J = 2.05 Hz, 1 H, C=CHH), 7.17 (m, 5 H, arom. H). ^¹³C NMR (125 MHz, CDCl₃): δ = 15.87 (cis), 20.30 (trans), 38.58, 51.75, 70.78, 81.29, 104.65, 115.70, 126.64, 128.81, 129.44, 130.05, 140.08, 152.57. GC-MS [t _R = 10.70 min(trans), 6.71 min(cis)]: m/z (%) = 188 (5) [M]⁺, 143 (17), 129 (100), 97 (70).
Compound 1bb: ^¹H NMR (500 MHz, CDCl₃): δ = 0.96
(d, J = 6.31 Hz, 3 H, CH₃), 2.41 (s, 3 H, SCH₃), 2.58 (dd, J = 14.03, 8.04 Hz, 2 H, CH₂Ar), 2.81 (dd, J = 14.19, 6.13 Hz, 1 H, 3-H), 3.66 (quint, J = 6.38 Hz, 1 H, 2-H), 4.19 (q, J = 2.21 Hz, 1 H, 5-H), 4.21 (q, J = 2.21 Hz, 1 H, 5-H), 4.78 (q, J = 2.36 Hz, 1 H, C=CHH), 4.87 (q, J = 2.21 Hz, 1 H, C=CHH), 7.13 (m, 4 H, arom. H.). ^¹³C NMR (125 MHz, CDCl₃): δ = 11.12, 21.17, 38.03, 44.76, 70.85, 79.92, 114.87, 127.57, 128.73, 130.37, 138.39, 149.53. GC-MS
[t _R = 10.70 min, 9.09 min(trans), 9.30 min(cis)]: m/z (%) = 234 (12) [M]⁺, 137 (100), 122 (8).
Compound 1bc: ^¹H NMR (500 MHz, CDCl₃): δ = 0.96 (d, J = 6.31 Hz, 3 H, CH₃), 2.41 (m, 1 H, CHHPh), 2.59 (m, 1 H, CHHPh), 2.81 (dd, J = 14.03, 6.46 Hz, 1 H, 3-H), 3.66 (quint, J = 6.31 Hz, 1 H, 2-H), 4.20 (dq, J _d = 13.24 Hz, J _q = 2.21 Hz, 1 H, 5-H), 4.34 (dt, J _d = 13.03 Hz, J _t = 1.85 Hz, 1 H, 5-H), 4.76 (q, J = 2.21 Hz, 1 H, C=CHH), 4.78 (q, J = 2.21 Hz, 1 H, C=CHH), 7.07 (m, 2 H, o-arom. H), 7.19 (m, 2 H, m-arom. H). ^¹³C NMR (125 MHz, CDCl₃): δ = 20.33, 37.92, 51.69, 70.81, 81.07, 104.89, 128.92, 130.77, 132.92, 138.55, 153.58. GC-MS [t _R = 7.75 min(trans), 7.98 min(cis)]: m/z (%) = 222 (1) [M]⁺, 143 (70), 125 (100), 97 (75).
Compound 1ca: ^¹H NMR (500 MHz, CDCl₃): δ = 0.71 (d, J = 6.94 Hz, 3 H, CH₃), 0.78 (d, J = 6.94 Hz, 3 H, CH₃), 1.48 (m, 1 H, CHCH₃), 2.71 (m, 2 H, CH₂Ph), 3.39 (m, 1 H, 3-H), 3.42 (m, 1 H, 2-H), 4.26 (m, 2 H, 5-H), 4.67 (d, J = 2.21 Hz, 1 H, C=CHH), 4.83 (d, J = 1.58 Hz, 1 H, C=CHH), 7.23 (m, 5 H, arom. H). ^¹³C NMR (125 MHz, CDCl₃): δ = 17.93, 19.60, 31.63, 40.89, 48.30, 70.88, 89.81, 105.17, 126.57, 127.66, 128,68, 129.65, 140.31, 141.65, 152.27. GC-MS
[t _R = 7.21 min(trans), 7.31 min(cis)]: m/z (%) = 216 (7) [M]⁺, 173 (15), 155 (45), 143 (45), 129 (85), 91 (100). Compound 2: ^¹H NMR (500 MHz, CDCl₃): δ = 2.73 (m, 1 H, 3-H), 2.92 (m, 2 H, CH₂Ph), 3.84 (d, J = 17.34 Hz, 1 H, 5-H), 4.25 (d, J = 16.08 Hz, 1 H, 5-H), 4.73 (d, J = 9.48 Hz,
1 H, 2-H), 7.30 (m, 10 H, arom. H). ^¹³C NMR (125 MHz, CDCl₃): δ = 32.58, 56.36, 72.13, 84.00, 126.80, 127.07, 129.07, 129.76, 130.25, 131.88, 140.08, 142.04, 216.12. GC-MS (t _R = 9.91 min): m/z (%) = 252 (1) [M]⁺, 193 (10), 161 (100).
Compound 9: ^¹H NMR (500 MHz, CDCl₃): δ = 2.68 (m, 2 H, CH₂Ph), 3.28 (m, 1 H, 5-H), 4.55 (d, J = 10.09 Hz, 1 H, 6-H), 5.18 (d, J = 5.67 Hz, 1 H, 2-H), 5.35 (d, J = 5.67 Hz,
1 H, 2-H), 7.22 (m, 10 H, arom. H). ^¹³C NMR (125 MHz, CDCl₃): δ = 33.30, 49.61, 80.49, 93.20, 127.34, 127.81, 129.11, 129.41, 129.76, 129.99, 137.93, 137.97, 170.04. GC-MS (t _R = 10.82 min): m/z (%) = 268 (13) [M]⁺, 238 (13), 193 (22) [M], 176 (72), 91 (100).