Chloroesterification of Enynes Catalyzed by NHC Rhodium Compounds

Abstract

An efficient rhodium N-heterocyclic carbene (NHC)-catalyzed chloroesterification of terminal alkynes and enynes has been developed. The reaction was highly regio- and stereospecific: the Z-isomer was obtained as the sole product.

N-heterocyclic carbene - rhodium - catalysis - chloroesterification - enyne

References and Notes

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General Procedure for Rh-NHC-Catalyzed Chloroesterification of Alkyne: To an oven-dried 10-mL tube containing toluene (5 mL), Rh-NHC (14 mg, 1 mol%) and alkyne (0.7 mmol) were added sequentially. After sealing the tube, the reaction temperature was elevated to 100 °C. The reaction was carried out in a test tube capped with a rubber septum. The rubber septum was tied with an aluminum binder. Thus, the reaction could be monitored by taking a small amount of the reaction mixture using a syringe. After the reactant was consumed, the solvent was removed under reduced pressure. Flash column chromatography gave the product.
3ab: ¹H NMR (300 MHz, CDCl₃): δ = 1.33 (t, J = 7.1 Hz, 3 H), 1.61 (m, 2 H), 1.71 (dd, J = 5.4, 9.2 Hz, 2 H), 2.25 (d, J = 4.1 Hz, 4 H), 4.22 (q, J = 7.1 Hz, 2 H), 6.11 (s, 1 H), 6.76 (t, J = 3.6 Hz, 1 H). ¹³C NMR (75 MHz, CDCl₃): δ = 14.4, 21.7, 22.6, 26.4, 60.5, 112.9, 133.6, 136.0, 148.9, 165.0. HRMS (EI): m/z calcd for C₁₁H₁₅ClO₂: 214.0761; found: 214.0764. IR: 1414 (w), 1433 (w), 1539 (w), 1601 (s), 1720 (s), 2120 (w), 2240 (w), 2296 (s), 2400 (w), 2504 (w), 2672 (m), 2920 (s), 2984 (m), 3048 (s), 3408 (br), 3680 (w), 3736 (w), 3936 (w) cm^-1.
3ac: ¹H NMR (300 MHz, CDCl₃): δ = 1.58 (m, 2 H), 1.68 (m, 2 H), 2.22 (d, J = 6.0 Hz, 4 H), 6.15 (s, 1 H), 6.77 (s, 1 H), 7.35 (m, 5 H) ¹³C NMR (75 MHz, CDCl₃): δ = 21.6, 22.5, 26.3, 66.3, 112.4, 128.3, 128.5, 128.7, 133.6, 136.0, 136.4, 147.6, 164.1. HRMS (EI): m/z calcd for C₁₅H₁₅ClO₂: 262.0761; found: 262.0755. IR: 1416 (w), 1454 (w), 1486 (w), 1595 (s), 1723 (s), 1764 (w), 2128 (w), 2304 (s), 2408 (w), 2512 (w), 2672 (w), 2864 (w), 2928 (m), 2976 (w), 3048 (s), 3400(br), 3680 (w), 3744 (w), 3936 (m) cm^-1.
3ba: ¹H NMR (300 MHz, CDCl₃): δ = 3.78 (s, 3 H), 6.20 (s, 1 H), 6.82 (d, J = 15.3 Hz, 1 H), 7.25-7.38 (m, 4 H), 7.47-7.50 (m, 2 H). ¹³C NMR (75 MHz, CDCl₃): δ = 51.8, 117.8, 125.9, 127.8, 129.1, 129.7, 135.4, 138.9, 144.6, 164.9. HRMS (EI): m/z calcd for C₁₂H₁₁ClO₂: 222.0447; found: 222.0445. IR: 1416 (w), 1596 (w), 1723 (s), 2296 (m), 2968 (s), 3048 (s) cm^-1.
3da: ¹H NMR (300 MHz, CDCl₃): δ = 3.77 (s, 3 H), 3.83 (s, 3 H), 6.70 (d, J = 15.2 Hz, 2 H), 6.90 (d, J = 7.0 Hz, 2 H), 7.32 (d, J = 15.2 Hz, 1 H), 7.42 (d, J = 7.0 Hz, 2 H). ¹³C NMR (75 MHz, CDCl₃): δ = 51.7, 55.6, 114.6, 116.6, 123.8, 128.2, 129.4, 138.6, 145.1, 161.0, 165.1. HRMS (EI): m/z calcd for C₁₃H₁₃ClO₃: 252.0553; found: 252.0555. IR: 1539 (w), 1584 (w), 1721 (s), 2296 (m), 2968 (s), 3048 (s) cm^-1.
3ea: ¹H NMR (300 MHz, CDCl₃): δ = 2.02 (s, 3 H), 3.78 (s, 3 H), 5.43 (s, 1 H), 5.92 (s, 1 H), 6.24 (s, 1 H). ¹³C NMR (75 MHz, CDCl₃): δ = 20.7, 51.9, 115.7, 122.9, 139.7, 146.1, 165.1. HRMS (EI): m/z calcd for C₇H₉Cl₁O₂: 160.0291; found: 160.0294. IR: 1417 (w), 1435 (w), 1596 (m), 1729 (s), 2296 (s), 2400 (w), 2572 (w), 2672 (w), 2976 (m), 3048 (s), 3416 (br), 3672 (w), 3736 (w), 3928 (m) cm^-1.
3ga: ¹H NMR (300 MHz, CDCl₃): δ = 0.00 (s, 6 H), 0.84 (s, 9 H), 3.67 (s, 3 H), 4.28 (m, 2 H), 6.01 (s, 1 H), 6.34 (m, 1 H), 6.54 (td, J = 3.7, 14.7 Hz, 1 H). ¹³C NMR (75 MHz, CDCl₃): δ = -5.2, 18.6, 26.0, 26.1, 51.7, 62.6, 117.1, 126.4, 140.8, 144.3, 165.1. HRMS (FAB): m/z calcd for C₁₂H₂₃ClO₃Si: 290.1105; found: 291.1185. IR: 1420 (br), 1460 (w), 1603 (s), 1640 (w), 1728 (s), 2304 (m), 2400 (w), 2512 (w), 2672 (w), 2848 (w), 2944 (s), 3056 (m), 3360 (br), 3672 (w), 3736 (w), 3936 (w) cm^-1.

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<A NAME="RU07907ST-16">16</A> One of the referees suggested the possibility of the formation of an alkynic ester in the cases where low activities for the chloroesterification were observed (entries 4, 8, and 12 in Table 2): Nozaki K. Sato N. Takaya H. Bull. Chem. Soc. Jpn.  1996,  69:  1629 ; however, no other by-products, except the trimerized product, were found