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Synlett 2007(9): 1426-1430  
DOI: 10.1055/s-2007-980372
LETTER
© Georg Thieme Verlag Stuttgart · New York

Enantioselective Synthesis of C 2-Symmetric Dimethyl Cyclohexadiene­dicarboxylates through Cationic Rhodium(I)/Modified-BINAP-Catalyzed [2+2+2] Cycloadditions

Ken Tanaka*, Goushi Nishida, Hiromi Sagae, Masao Hirano
Department of Applied Chemistry, Graduate School of Engineering, Tokyo University of Agriculture and Technology, Koganei, Tokyo 184-8588, Japan
Fax: +81(42)3887037; e-Mail: tanaka-k@cc.tuat.ac.jp;
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Publication History

Received 22 March 2007
Publication Date:
23 May 2007 (online)

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Abstract

A cationic rhodium(I)/(S)-Tol-BINAP complex was employed to catalyze an enantioselective intramolecular [2+2+2] cycloaddition of a trans enediyne leading to a C 2-symmetric tricyclic dimethyl cyclohexadienedicarboxylate in 95% yield with 59% ee. A cationic rhodium(I)/(R)-H8-BINAP complex was employed to catalyze an intermolecular [2+2+2] cycloaddition of 1,6-diynes with dimethyl fumarate leading to C 2-symmetric bicyclic dimethyl ­cyclohexadienedicarboxylates in 35-96% yields with ee values of 82-98%.

Key words

asymmetric catalysis - BINAP - cycloadditions - cyclohexadienes - rhodium

    References and Notes

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16

General Procedure for Intramolecular [2+2+2] Cycloadditions (Table 1): Under an Ar atmosphere, BINAP-type ligand (0.0125 mmol) and [Rh(cod)2]BF4 (cod: 1,5-cyclooctadiene; 0.0125 mmol) were dissolved in CH2Cl2 (2.0 mL) and the mixture was stirred at r.t. for 5 min. H2 (1 atm) was introduced to the resulting solution in a Schlenk tube. After stirring at r.t. for 0.5 h, the resulting solution was concentrated and redissolved in CH2Cl2 (8.0 mL). To this solution was added dropwise over 10 min a solution of 1 (0.125 mmol) in CH2Cl2 (2.0 mL), and the remaining substrate was washed away by using CH2Cl2 (2.5 mL). After stirring at r.t. for 16 h, the resulting solution was concentrated and product 2 was isolated by preparative TLC. Product (-)-2a: [α]25 D -31.0° (acetone, c = 0.010; 48% ee). IR (neat): 3390, 2930, 2860, 2360, 1730, 1680, 1040, 900 cm-1. 1H NMR (300 MHz, CDCl3): δ = 5.86 (s, 2 H), 4.55 (d, J = 13.8 Hz, 2 H), 4.35 (d, J = 13.8 Hz, 2 H), 4.23-4.31 (m, 2 H), 3.41-3.53 (m, 2 H), 2.63-2.81 (m, 2 H). HRMS (ESI): m/z [M]+ calcd for C10H12O2: 164.0837; found: 164.0841. HPLC: CHIRALPAK AD-H; hexane-i-PrOH = 99:1; 1.0 mL/min, t R = 12.6 min (major isomer), t R = 13.5 min (minor isomer). Product (+)-2b: [α]25 D +64.9° (acetone, c = 0.665, 59% ee). IR (neat): 3390, 2950, 2850, 1720, 1440, 1300, 1210, 1150, 1020, 920 cm-1. 1H NMR (300 MHz, CDCl3): δ = 4.98 (d, J = 17.4 Hz, 2 H), 4.52 (d, J = 17.4 Hz, 2 H), 4.25-4.36 (m, 2 H), 3.76 (s, 6 H), 3.41-3.50 (m, 2 H), 2.84-3.02 (m, 2 H). 13C NMR (CDCl3, 75 MHz): δ = 165.4, 155.8, 120.5, 72.8, 70.3, 51.9, 45.4. HRMS (ESI): m/z [M]+ calcd for C14H16O6: 280.0947; found: 280.0988. HPLC: CHIRALPAK AS; hexane-2-PrOH = 95:5; 1.0 mL/min;
t R = 29.3 min (major isomer), t R = 39.0 min (minor isomer).

17

General Procedure for Intermolecular [2+2+2] Cycloadditions (Table 2): Under an Ar atmosphere, BINAP-type ligand (0.010 mmol) and [Rh(cod)2]BF4 (0.010 mmol) were dissolved in CH2Cl2 (2.0 mL) and the mixture was stirred at r.t. for 5 min. H2 (1 atm) was introduced to the resulting solution in a Schlenk tube. After stirring at r.t. for 0.5 h, the resulting solution was concentrated and redissolved in CH2Cl2 (0.5 mL). To this solution was added a CH2Cl2 (0.5 mL) solution of 13 (1.00 mmol) and then a CH2Cl2 (1.0 mL) solution of 12 (0.20 mmol) was added dropwise over 20 min at r.t. After stirring at r.t. for 1 h, the resulting solution was concentrated and product 14 was isolated by preparative TLC. Product (-)-14a: mp 41.0-41.9 °C; [α]25 D -334.7° (c = 1.53, CHCl3; 90% ee). IR (neat): 2953, 1731, 1434, 1253, 1206, 1169, 1007 cm-1. 1H NMR (300 MHz, CDCl3): δ = 4.50 (d, J = 12.9 Hz, 2 H), 4.43 (d, J = 12.9 Hz, 2 H), 3.68 (s, 6 H), 3.55 (s, 2 H), 1.82 (s, 6 H). 13C NMR (75 MHz, CDCl3): δ = 172.7, 132.4, 117.3, 70.0, 52.2, 47.8, 19.2. HPLC: CHIRALCEL OD-H, hexane-i-PrOH = 97:3; 1.0 mL/min; t R = 10.2 min (minor isomer),
t R = 11.8 min (major isomer). Product (-)-14b: mp 128.9-130.5 °C; [α]25 D -175.2° (c = 4.78, CHCl3; 82% ee). IR (neat): 2952, 1732, 1430, 1346, 1305, 1259, 1160 cm-1. 1H NMR (300 MHz, CDCl3): δ = 7.73 (d, J = 7.8 Hz, 2 H), 7.35 (d, J = 7.8 Hz, 2 H), 3.98 (d, J = 12.6 Hz, 2 H), 3.91 (d, J = 12.6 Hz, 2 H), 3.91 (s, 6 H), 3.52 (s, 2 H), 2.44 (s, 3 H), 1.81 (s, 6 H). 13C NMR (75 MHz, CDCl3): δ = 172.1, 143.6, 132.9, 129.7, 129.0, 127.6, 120.0, 52.2, 50.1, 47.2, 21.4, 19.1. HPLC: CHIRALPAK AD-H, hexane-i-PrOH = 90:10; 1.0 mL/min; t R = 21.0 min (major isomer), t R = 23.5 min (minor isomer). Product (-)-14c: [α]25 D -229.0° (c = 0.59, CHCl3; 98% ee). IR (neat): 2954, 1733, 1435, 1253, 1201, 1165 cm-1. 1H NMR (300 MHz, CDCl3): δ = 3.72 (s, 6 H), 3.66 (s, 6 H), 3.50 (s, 2 H), 3.01 (d, J = 16.5 Hz, 2 H), 2.94 (d, J = 16.5 Hz, 2 H), 1.85 (s, 6 H). 13C NMR (75 MHz, CDCl3): δ = 172.9, 171.8, 132.4, 119.8, 58.7, 52.8, 52.1, 47.9, 37.1, 19.2. HPLC: CHIRALPAK AD-H, hexane-i-PrOH = 97:3; 1.0 mL/min; t R = 12.5 min (major isomer),
t R = 15.9 min (minor isomer).

18

Products 16 and (-)-17: [α]25 D -25.3° {CHCl3, c = 0.160 [based on the calculated content of (-)-17], >99% ee}. 1H NMR (300 MHz, CDCl3): δ = 3.81 (d, J = 12.6 Hz, 2 H, 17), 3.80 (d, J = 12.6 Hz, 2 H, 16), 3.58 (d, J = 12.6 Hz, 2 H, 17), 3.57 (d, J = 12.6 Hz, 2 H, 16), 3.43 (d, J = 9.0 Hz, 2 H, 17), 3.27 (d, J = 9.0 Hz, 2 H, 16), 2.74 (d, J = 9.0 Hz, 2 H, 17), 2.59 (d, J = 9.0 Hz, 2 H, 16), 2.44 (s, 6 H, 16), 2.43 (s, 6 H, 17), 1.48-1.63 (m, 2 H + 2 H, 16 + 17), 1.19-1.33 (m, 2 H + 2 H, 16 + 17), 0.90 (s, 6 H + 6 H, 16 + 17). HPLC: CHIRALPAK AD-H, hexane-i-PrOH = 90:10; 1.0 mL/min; t R = 81.8 min [minor dl-isomer (+)-17], t R = 98.5 min (meso-isomer 16), t R = 109.8 min [major dl-isomer (-)-17].