Supplementary Figure 1. 1 H and 13 C NMR spectra for compound 1a

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1 Supplementary Figure 1. 1 H and 13 C NMR spectra for compound 1a

2 Supplementary Figure 2. 1 H and 13 C NMR spectra for compound 1b

3 n-pr 1c n-pr 1c Supplementary Figure 3. 1 H and 13 C NMR spectra for compound 1c

4 Supplementary Figure 4. 1 H and 13 C NMR spectra for compound 1d

5 n-bu 1e n-bu 1e Supplementary Figure 5. 1 H and 13 C NMR spectra for compound 1e

6 Bn 1f Bn 1f Supplementary Figure 6. 1 H and 13 C NMR spectra for compound 1f

7 Ph 1g Ph 1g Supplementary Figure 7. 1 H and 13 C NMR spectra for compound 1g

8 Supplementary Figure 8. 1 H and 13 C NMR spectra for compound 1h

9 Ph 1i Ph 1i Supplementary Figure 9. 1 H and 13 C NMR spectra for compound 1i

10 Supplementary Figure H and 13 C NMR spectra for compound 1j

11 F 1k F 1k Supplementary Figure H and 13 C NMR spectra for compound 1k

12 Supplementary Figure H and 13 C NMR spectra for compound 1l

13 Me 1m Me 1m Supplementary Figure H and 13 C NMR spectra for compound 1m

14 n n Supplementary Figure H and 13 C NMR spectra for compound 1n

15 Supplementary Figure H and 13 C NMR spectra for compound 1o

16 Supplementary Figure H and 13 C NMR spectra for compound 1p

17 Me Me 6a Me Me 6a Supplementary Figure H and 13 C NMR spectra for compound 6a

18 Et Me 6b Et Me 6b Supplementary Figure H and 13 C NMR spectra for compound 6b

19 Supplementary Figure H and 13 C NMR spectra for compound 6c

20 Supplementary Figure H and 13 C NMR spectra for compound 6d

21 Supplementary Figure H and 13 C NMR spectra for compound 6e

22 Me 6f Me 6f Supplementary Figure H and 13 C NMR spectra for compound 6f

23 Supplementary Figure H and 13 C NMR spectra for compound 6g

24 Supplementary Figure H and 13 C NMR spectra for compound 6h

25 Supplementary Figure H and 13 C NMR spectra for compound 8

26 Me 2a Me 2a Supplementary Figure H and 13 C NMR spectra for compound 2a

27 Et 2b Et 2b Supplementary Figure H and 13 C NMR spectra for compound 2b

28 n-pr 2c n-pr 2c Supplementary Figure H and 13 C NMR spectra for compound 2c

29 Supplementary Figure H and 13 C NMR spectra for compound 2d

30 n-bu 2e n-bu 2e Supplementary Figure H and 13 C NMR spectra for compound 2e

31 Supplementary Figure H and 13 C NMR spectra for compound 2f

32 Supplementary Figure H and 13 C NMR spectra for compound 2g

33 Me 2 C 2h Me 2 C 2h Supplementary Figure H and 13 C NMR spectra for compound 2h

34 Ph 2i Ph 2i Supplementary Figure H and 13 C NMR spectra for compound 2i

35 NC 2j NC 2j Supplementary Figure H and 13 C NMR spectra for compound 2j

36 Supplementary Figure H and 13 C NMR spectra for compound 2k

37 Cl 2l Cl 2l Supplementary Figure H and 13 C NMR spectra for compound 2l

38 Supplementary Figure H and 13 C NMR spectra for compound 2m

39 Supplementary Figure H and 13 C NMR spectra for compound 2n

40 o o Supplementary Figure H and 13 C NMR spectra for compound 2o

41 Supplementary Figure H and 13 C NMR spectra for compound 2p

42 Me 7a Me Me 7a Me Supplementary Figure H and 13 C NMR spectra for compound 7a

43 Me 7b Et Me 7b Et Supplementary Figure H and 13 C NMR spectra for compound 7b

44 Me 7c Me 7c Supplementary Figure H and 13 C NMR spectra for compound 7c

45 Me 7d n-bu Me 7d n-bu Supplementary Figure H and 13 C NMR spectra for compound 7d

46 Ph Me 7e Ph Me 7e Supplementary Figure H and 13 C NMR spectra for compound 7e

47 Supplementary Figure H and 13 C NMR spectra for compound 7f

48 Supplementary Figure H and 13 C NMR spectra for compound 7h

49 Supplementary Figure H and 13 C NMR spectra for compound 9

50 Supplementary Figure H and 13 C NMR spectra for compound 10

51 H H Ph n-bu 13 N Ts C 2 Me H H Ph n-bu 13 N Ts C 2 Me Supplementary Figure H and 13 C NMR spectra for compound 13

52 Supplementary Figure 52. CSY spectra for compound 13 Supplementary Figure 53. HMBC spectra for compound 13

53 Supplementary Figure 54. HMQC spectra for compound 13 H H H H N Ts CH 3 Supplementary Figure 55. NESY spectra for compound 13

54 Me 6g Racemic 6g ptically pure 6g-1 Recover of 6g-1 for compound 6g obtained via by use of a chiral Supplementary Figure 56. HPLC spectra stationary phase column (see Supplementary methods) )

55 Mee 2a Racemic 2a Enantiomerically enriched 2a Supplementary Figure 57. HPLC spectraa for compound 2a

56 Ett 2b Racemic 2b Enantiomerically enriched 2b Supplementary Figure 58. HPLC spectraa for compound 2b

57 n-pr 2c Racemic 2c Enantiomerically enriched 2c Supplementary Figure 59. HPLC spectraa for compound 2c

58 i-pr 2d Racemic 2d Enantiomerically enriched 2d Supplementary Figure 60. HPLC spectraa for compound 2d

59 n-bu 2e Racemic 2e Enantiomerically enriched 2e Supplementary Figure 61. HPLC spectraa for compound 2e

60 Bnn 2f Racemic 2f Enantiomerically enriched 2f Supplementary Figure 62. HPLC spectraa for compound 2f

61 Ph 2g Racemic 2g Enantiomerically enriched 2g Supplementary Figure 63. HPLC spectraa for compound 2g

62 Me 2 C 2h Racemic 2h Enantiomerically enriched 2h Supplementary Figure 64. HPLC spectraa for compound 2h

63 Phh 2i Racemic 2i Enantiomerically enriched 2i Supplementary Figure 65. HPLC spectraa for compound 2i

64 NC 2j Racemic 2j Enantiomerically enriched 2j Supplementary Figure 66. HPLC spectraa for compound 2j

65 F 2k Racemic 2k Enantiomerically enriched 2k Supplementary Figure 67. HPLC spectraa for compound 2k

66 Cl 2l Racemic 2l Enantiomerically enriched 2l Supplementary Figure 68. HPLC spectraa for compound 2l

67 Me 2m Racemic 2m Enantiomerically enriched 2m Supplementary Figure 69. HPLC spectraa for compound 2m

68 2n Racemic 2n Enantiomerically enriched 2n Supplementary Figure 70. HPLC spectraa for compound 2n

69 2o Racemic 2o Enantiomerically enriched 2o Supplementary Figure 71. HPLC spectraa for compound 2o

70 Mee Me 2p Me Racemic 2p Chiral 2pp before recrystallization Enantiomerically enriched 2p after recrystallization Supplementary Figure 72. HPLC spectraa for compound 2p

71 Me Me 7a Racemic 7a Enantiomerically enriched 7a ptically pure 7a after Recrystallization 7a Supplementary Figure 73. HPLC spectraa for compound 7a

72 Et Me 7b Racemic 7b Enantiomerically enriched 7b Supplementary Figure 74. HPLC spectraa for compound 7b

73 Mee 7c Racemic 7c Enantiomerically enriched 7c 7c 7c Supplementary Figure 75. HPLC spectraa for compound 7c

74 Me 7d n-bu Racemic 7d Enantiomerically enriched 7d Supplementary Figure 76. HPLC spectraa for compound 7d

75 Ph Me 7e Racemic 7e Enantiomerically enriched 7e Supplementary Figure 77. HPLC spectraa for compound 7e

76 Me 7f Racemic 7f Enantiomerically enriched 7f Supplementary Figure 78. HPLC spectraa for compound 7f

77 Ph 7h Racemic 7h Enantiomerically enriched 7h Supplementary Figure 79. HPLC spectraa for compound 7h

78 Mee 9 Me Racemic 9 Enantiomerically enriched 9 Supplementary Figure 80. HPLC spectraa for compound 9

79 Me Me 10 Racemic 10 Enantiomerically enriched 10 Supplementary Figure 81. HPLC spectraa for compound 10

80 H H Ph n-bu 13 N Ts C 2 Me Racemic 13 Enantiomerically enriched 13 Supplementary Figure 82. HPLC spectraa for compound 13

81 Supplementary Table 1. Crystal data and structure refinement for 2a Empirical formula C 11 H 10 3 Formula weight Temperature Wavelength Crystal system Space group 100(2) K Å Triclinic P1 Unit cell dimensions a = (4) Å a= (10). b = (4) Å b= (10). c = (6) Å g = (10). Volume (5) Å 3 Z 2 Density (calculated) Mg/m 3 Absorption coefficient mm -1 F(000) 200 Crystal size x x mm 3 Theta range for data collection to Index ranges -8<=h<=8, -9<=k<=8, -11<=l<=11 Reflections collected Independent reflections 3494 [R(int) = ] Completeness to theta = % Absorption correction Semi-empirical from equivalents Max. and min. transmission and Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 3494 / 6 / 268 Goodness-of-fit on F Final R indices [I>2sigma(I)] R1 = , wr2 = R indices (all data) R1 = , wr2 = Absolute structure parameter 0.07(2) Extinction coefficient 0.050(4) Largest diff. peak and hole and e.å -3

82 Supplementary Table 2. Crystal data and structure refinement for 2n Empirical formula C 20 H 14 3 Formula weight Temperature Wavelength Crystal system 100(2) K Å rthorhombic Space group P Unit cell dimensions a = (3) Å a= 90. b = (4) Å b= 90. c = (10) Å g = 90. Volume (11) Å 3 Z 4 Density (calculated) Mg/m 3 Absorption coefficient mm -1 F(000) 632 Crystal size x x mm 3 Theta range for data collection to Index ranges -9<=h<=8, -11<=k<=11, -20<=l<=24 Reflections collected 9213 Independent reflections 2748 [R(int) = ] Completeness to theta = % Absorption correction Semi-empirical from equivalents Max. and min. transmission and Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 2748 / 1 / 215 Goodness-of-fit on F Final R indices [I>2sigma(I)] R1 = , wr2 = R indices (all data) R1 = , wr2 = Absolute structure parameter -0.06(6) Extinction coefficient n/a Largest diff. peak and hole and e.å -3

83 Supplementary Table 3. Crystal data and structure refinement for 7b Empirical formula C 14 H 16 3 Formula weight Temperature Wavelength Crystal system 100(2) K Å rthorhombic Space group P Unit cell dimensions a = (4) Å a= 90. b = (4) Å b= 90. c = (15) Å g = 90. Volume (12) Å 3 Z 4 Density (calculated) Mg/m 3 Absorption coefficient mm -1 F(000) 496 Crystal size x x mm 3 Theta range for data collection to Index ranges -7<=h<=7, -9<=k<=6, -32<=l<=31 Reflections collected Independent reflections 2416 [R(int) = ] Completeness to theta = % Absorption correction Semi-empirical from equivalents Max. and min. transmission and Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 2416 / 0 / 173 Goodness-of-fit on F Final R indices [I>2sigma(I)] R1 = , wr2 = R indices (all data) R1 = , wr2 = Absolute structure parameter 0.11(5) Extinction coefficient n/a Largest diff. peak and hole and e.å -3

84 Supplementary Note 1 Crystal data of all these crystals CCDC No (2a), (2n) and (7b) were collected on a Bruker AXS D8 Venture equipped with a Photon 100 CMS active pixel sensor detector using graphite-monochromated Cu-Kα radiation (λ = Å) using a sealed tube. Absorption corrections were made with the program SADABS 1, and the crystallographic package SHELXTL 2,3 was used for all calculations. 2a at 100(2) K: C 11 H 10 3, FW = , triclinic, P1; a = (4) Å, b = (4) Å, c = (6) Å, = (10), = (10), = (10), V = (5) Å 3, Z = 2, calc = g cm 3, μ = 0.82 mm 1, GF = 1.073, final R 1 = , wr 2 = [for 3492 data I > 2σ(I)]. Flack parameter, 0.09(14) and Parson, 0.066(23). There are two formula units in the asymmetric unit. The coordinates of the hydrogen atoms for C10A and C10B were refined with SADI option as the AFIX 93 did not work probably for the allylic group. However a riding model was used for the thermal parameters of the H atoms. The absolute structure parameter and chirality could not be determined reliably as the compound does not have heavier elements. 2n at 100(2) K: C 20 H 14 3, FW = , orthorhombic, P ; a = (3) Å, b = (4) Å, c = (10) Å, V = (11) Å 3, Z = 2, calc = g cm 3, μ = mm 1, GF = 1.064, final R 1 = , wr 2 = [for 2689 data I > 2σ(I)]. Flack parameter, -0.12(24) and Parson, 0.058(57). The coordinates of the hydrogen atoms for C20 were refined with SADI option as the AFIX 93 did not work probably for the allylic group. However a riding model was used for the thermal parameters of the H atoms. The absolute structure parameter and chirality could not be determined reliably as the compound does not have heavier elements. 7b at 100(2) K: C 14 H 16 3, FW = , orthorhombic, P ; a = (4) Å, b = (4) Å, c = (10) Å, V = (12) Å 3, Z = 4, calc = g cm 3, μ = mm 1, GF = 1.098, final R 1 = , wr 2 = [for 2399 data I > 2σ(I)]. Flack parameter, 0.11(5) and Parson, 0.048(27). The absolute structure parameter and chirality could not be determined reliably as the compound does not have heavier elements.

85 Supplementary Methods General Information Unless otherwise specified, all reactions were carried out under a nitrogen atmosphere, with dry, freshly distilled solvents in anhydrous conditions. THF, ether and toluene were distilled from sodium; while CH 2 Cl 2 and MeCN were distilled from CaH 2 and ethyl acetate (Ea) and CHCl 3 were used without further purification. All chemicals were used without further purification as commercially available unless otherwise noted. Thin-layer chromatography (TLC) was performed on silica gel plates (60F-254) using UV-light (254 and 365 nm). Flash chromatography was conducted on silica gel ( mesh). 1 H and 13 C NMR spectra were recorded on a Bruker AMX500 (500 MHz) spectrometer. Chemical shifts were reported in parts per million (ppm). All high resolution mass spectra were obtained on a Finnigan/MAT 95XL-T spectrometer. ptical rotations were measured using a Jasco DIP 1000 polarimeter. Enantiomeric excesses were determined by HPLC analysis on a chiral stationary phase. The racemic sample was prepared by DABC catalysis. Representative procedure for the synthesis of allenoates 1, 6 and 8 Allenoates 1, 6 and 8 were synthesized by reacting in-situ prepared allenic acid chloride A2 with the corresponding tert-alcohol S1 4 8, which were easily accessible from the corresponding phenols. To a stirred solution of allenic acid A1 9 (2.2 mmol) in anhydrous CH 2 Cl 2 (10 ml) under N 2 atmosphere at room temperature was added oxalyl chloride (2.2 mmol, 189 L), followed by DMF (5 L). The resulting mixture was stirred further 1 h and was used directly in the next step. To a flame dried round bottle flask with a magnetic stirring bar under N 2 were added tert-alcohol S1 (2.0 mmol) and Et 3 N (2.0 mmol, 278 L), followed by anhydrous CH 2 Cl 2 (10 ml). The resulting mixture was cooled to 20 o C, and the above A2 solution was added dropwise over 15 min under N 2 atmosphere. The reaction mixture was kept at 20 o C for 1 h and then at 10 o C for another 2 h. The reaction was then quenched with iced water, and extracted with CH 2 Cl 2 (2 30 ml). The combined organic extracts were washed by brine (50 ml) and concentrated. The residue was dissolved in EtAc (40 ml) and washed by 0.1 N NaH (20 ml), Brine (20 ml) successively. The organic phase was dried over Na 2 S 4, filtered and concentrated. The residue was purified directly by flash column chromatography to afford 1, 6 or 8 and recovered S1. Analytical data of allenoates 1, 6 and 8 1-Methyl-4-oxocyclohexa-2,5-dien-1-yl buta-2,3-dienoate (1a)

86 32% yield, white solid; 1 H NMR (500 MHz, CDCl 3 ) δ 6.91 (d, J = 10.1 Hz, 2H), 6.24 (d, J = 10.1 Hz, 2H), 5.60 (t, J = 6.5 Hz, 1H), 5.24 (d, J = 6.5 Hz, 2H), 1.58 (s, 3H); 13 C NMR (125 MHz, CDCl 3 ) δ 216.3, 185.0, 164.2, 149.0, 128.2, 87.7, 79.7, 74.7, HRMS (ESI) m/z calcd for C 11 H 10 Na 3 [M+Na] + = , found = Ethyl-4-oxocyclohexa-2,5-dien-1-yl buta-2,3-dienoate (1b) 29% yield, white solid; 1 H NMR (500 MHz, CDCl 3 ) δ 6.78 (d, J = 10.2 Hz, 2H), 6.22 (d, J = 10.2 Hz, 2H), 5.54 (t, J = 6.5 Hz, 1H), 5.18 (d, J = 6.5 Hz, 2H), 1.83 (q, J = 7.5 Hz, 2H), 0.85 (t, J = 7.5 Hz, 3H); 13 C NMR (125 MHz, CDCl 3 ) δ 216.2, 185.2, 164.1, 148.1, 129.1, 87.7, 79.5, 77.6, 32.3, 7.6. HRMS (ESI) m/z calcd for C 12 H 12 Na 3 [M+Na] + = , found = xo-1-propylcyclohexa-2,5-dien-1-yl buta-2,3-dienoate (1c) 27% yield, Colorless oil; 1 H NMR (500 MHz, CDCl 3 ) δ 6.85 (d, J = 10.2 Hz, 2H), 6.26 (d, J = 10.2 Hz, 2H), 5.59 (t, J = 6.5 Hz, 1H), 5.23 (d, J = 6.6 Hz, 2H), (m, 2H), (m, 2H), 0.91 (t, J = 7.4 Hz, 3H); 13 C NMR (125 MHz, CDCl 3 ) δ 216.3, 185.3, 164.1, 148.3, 128.9, 87.7, 79.5, 77.4, 41.4, 16.8, HRMS (ESI) m/z calcd for C 12 H 12 Na 3 [M+Na] + = , found = Isopropyl-4-oxocyclohexa-2,5-dien-1-yl buta-2,3-dienoate (1d) 17% yield, Pale yellow oil; 1 H NMR (500 MHz, CDCl 3 ) δ 6.79 (d, J = 10.3 Hz, 2H), 6.32 (d, J = 10.3 Hz, 2H), 5.59 (t, J = 6.5 Hz, 1H), 5.23 (d, J = 6.5 Hz, 2H), (m, 1H), 0.96 (d, J = 6.9 Hz, 6H); 13 C NMR (125 MHz, CDCl 3 ) δ 216.3, 185.4, 164.1, 147.1, 130.0, 87.8, 79.8, 79.5, 36.6, HRMS (ESI) m/z calcd for C 13 H 14 Na 3 [M+Na] + = , found = Butyl-4-oxocyclohexa-2,5-dien-1-yl buta-2,3-dienoate (1e)

87 31% yield, pale yellow oil; 1 H NMR (500 MHz, CDCl 3 ) δ 6.84 (d, J = 1.8 Hz, 2H), 6.27 (d, J = 10.2 Hz, 2H), 5.60 (t, J = 6.5 Hz, 1H), 5.24 (d, J = 6.5 Hz, 2H), (m, 2H), (m, 4H), 0.88 (t, J = 7.0 Hz, 3H); 13 C NMR (125 MHz, CDCl 3 ) δ 216.3, 185.3, 164.1, 148.3, 129.0, 87.8, 79.5, 77.4, 39.0, 25.4, 22. 7, 13.8; HRMS (ESI) m/z calcd for C 14 H 16 Na 3 [M+Na] + = , found = Benzyl-4-oxocyclohexa-2,5-dien-1-yl buta-2,3-dienoate (1f) 23% yield, white solid; 1 H NMR (500 MHz, CDCl 3 ) δ (m, 3H), (m, 2H), 6.80 (d, J = 10.2 Hz, 2H), 6.25 (d, J = 10.2 Hz, 2H), 5.58 (t, J = 6.5 Hz, 1H), 5.27 (d, J = 6.5 Hz, 2H), 3.07 (s, 2H); 13 C NMR (125 MHz, CDCl 3 ) δ 216.4, 184.9, 164.0, 148.3, 133.8, 131.0, 128.8, 128.2, 127.5, 87.7, 79.6, 76.5, HRMS (ESI) m/z calcd for C 17 H 14 Na 3 [M+Na] + = , found = xo-1-phenethylcyclohexa-2,5-dien-1-yl buta-2,3-dienoate (1g) 22% yield, pale yellow oil; 1 H NMR (500 MHz, CDCl 3 ) δ (m, 2H), (m, 1H), (m, 2H), 6.91 (d, J = 10.2 Hz, 2H), 6.32 (d, J = 10.2 Hz, 2H), 5.62 (t, J = 6.5 Hz, 1H), 5.26 (d, J = 6.5 Hz, 2H), (m, 2H), (m, 2H); 13 C NMR (125 MHz, CDCl 3 ) δ 216.4, 185.1, 164.0, 148.0, 140.5, 129.2, 128.6, 128.3, 126.4, 87.7, 79.6, 76.9, 41.2, HRMS (ESI) m/z calcd for C 18 H 16 Na 3 [M+Na] + = , found = (3-Methoxy-3-oxopropyl)-4-oxocyclohexa-2,5-dien-1-yl buta-2,3-dienoate (1h) 16% yield, pale yellow oil; 1 H NMR (500 MHz, CDCl 3 ) δ 6.80 (d, J = 10.0 Hz, 2H), 6.28 (d, J = 10.1 Hz, 2H), 5.58 (t, J = 6.5 Hz, 1H), 5.24 (d, J = 6.5 Hz, 2H), 3.65 (s, 3H), 2.33 (t, J = 7.8 Hz, 2H), 2.21 (dd, J = 8.7, 6.9 Hz, 2H); 13 C NMR (125 MHz, CDCl 3 ) δ 216.4, 184.8, 172.5, 163.9, 147.2, 129.8, 129.5, 87.5, 79.7, 76.3, 51.9, 33.9, 28.1; HRMS (ESI) m/z calcd for C 14 H 14 Na 5 [M+Na] + = , found =

88 4-xo-[1,1'-biphenyl]-1(4H)-yl buta-2,3-dienoate (1i) 18% yield, pale yellow solid; 1 H NMR (500 MHz, CDCl 3 ) δ (m, 2H), (m, 3H), 6.97 (d, J = 10.1 Hz, 2H), 6.35 (d, J = 10.1 Hz, 2H), 5.71 (t, J = 6.5 Hz, 1H), 5.32 (d, J = 6.5 Hz, 2H); 13 C NMR (125 MHz, CDCl 3 ) δ 216.5, 185.5, 163.7, 147.5, 136.3, 129.1, 128.8, 128.4, 128.2, 125.3, 87.9, 79.8, 77.7; HRMS (ESI) m/z calcd for C 16 H 11 3 [M-H] - = , found = '-Cyano-4-oxo-[1,1'-biphenyl]-1(4H)-yl buta-2,3-dienoate (1j) 18% yield, pale yellow solid; 1 H NMR (500 MHz, CDCl 3 ) δ 7.68 (d, J = 8.3 Hz, 2H), 7.56 (d, J = 8.6 Hz, 2H), 6.92 (d, J = 10.1 Hz, 2H), 6.39 (d, J = 9.9 Hz, 2H), 5.71 (t, J = 6.5 Hz, 1H), 5.35 (d, J = 6.5 Hz, 2H); 13 C NMR (125 MHz, CDCl 3 ) δ 216.7, 184.8, 163.3, 146.1, 141.8, 132.9, 129.0, 126.2, 118.1, 112.8, 105.0, 87.7, 80.0, 77.1; HRMS (ESI) m/z calcd for C 17 H 10 N 3 [M-H] - = , found = '-Fluoro-4-oxo-[1,1'-biphenyl]-1(4H)-yl buta-2,3-dienoate (1k) 16% yield, pale yellow solid; 1 H NMR (500 MHz, CDCl 3 ) δ 7.33 (td, J = 8.2, 5.9 Hz, 1H), 7.18 (ddd, J = 7.2, 4.2, 2.0 Hz, 2H), (m, 1H), 6.93 (d, J = 10.1 Hz, 2H), 6.34 (d, J = 10.1 Hz, 2H), 5.70 (t, J = 6.5 Hz, 1H), 5.33 (d, J = 6.5 Hz, 2H); 13 C NMR (125 MHz, CDCl 3 ) δ 216.6, 185.2, (d, J = Hz), 163.5, 146.8, (d, J = 7.3 Hz), (d, J = 8.2 Hz), 128.5, (d, J = 3.0 Hz), (d, J = 21.1 Hz), (d, J = 24.1 Hz), 87.8, 79.9; HRMS (ESI) m/z calcd for C 16 H 10 F 3 [M-H] - = , found = '-Chloro-4-oxo-[1,1'-biphenyl]-1(4H)-yl buta-2,3-dienoate (1l)

89 21% yield, pale yellow solid; 1 H NMR (500 MHz, CDCl 3 ) δ m, 4), 6.93 (d, J = 10.1 Hz, 2), (m, 2), 5.70 (t, J = 6.5 Hz, 1H), 5.32 (d, J = 6.5 Hz, 2); 13 C NMR (125MHz, CDCl 3 ) δ , 163.5, 147.0, 135.0, 134.8, 129.3, 128.4, , 87.8, 79.9, 77.2; HRMS (ESI) m/z calcd for C 16 H 11 ClNa 3 [M+Na] + = , found = '-Methyl-4-oxo-[1,1'-biphenyl]-1(4H)-yl buta-2,3-dienoate (1m) 14% yield, pale yellow oil; 1 H NMR (500 MHz, CDCl 3 ) δ 7.36 (d, J = 7.8 Hz, 1H), (m, 5H), 6.36 (d, J = 10.2 Hz, 2H), 5.66 (t, J = 6.5 Hz, 1H), 5.27 (d, J = 6.5 Hz, 2H), 2.52 (s, 3H); 13 C NMR (125 MHz, CDCl 3 ) δ 216.4, 185.2, 163.5, 145.5, 136.2, 134.7, 133.3, 129.1, 128.9, 126.6, 125.9, 87.9, 79.8, 78.6, 21.6; HRMS (ESI) m/z calcd for C 17 H 14 Na 3 [M+Na] + = , found = (Naphthalen-2-yl)-4-oxocyclohexa-2,5-dien-1-yl buta-2,3-dienoate (1n) 15% yield, pale yellow solid; 1 H NMR (500 MHz, CDCl 3 ) δ 7.97 (d, J = 1.2 Hz, 1H), 7.86 (d, J = 8.8 Hz, 1H), 7.82 (dd, J = 6.1, 3.4 Hz, 2H), (m, 2H), 7.47 (dd, J = 8.7, 1.9 Hz, 1H), 7.05 (d, J = 10.1 Hz, 2H), 6.40 (d, J = 10.1 Hz, 2H), 5.77 (t, J = 6.5 Hz, 1H), 5.36 (d, J = 6.5 Hz, 2H); 13 C NMR (125 MHz, CDCl 3 ) δ 216.6, 185.6, 163.7, 147.4, 133.4, 133.3, 133.1, 129.1, 128.4, 128.3, 127.7, 126.9, 126.8, 124.7, 122.7, 88.0, 79.8, 77.8; HRMS (ESI) m/z calcd for C 20 H 14 Na 3 [M+Na] + = , found = Ethynyl-4-oxocyclohexa-2,5-dien-1-yl buta-2,3-dienoate (1o) 28% yield, white solid; 1 H NMR (500 MHz, CDCl 3 ) δ 7.09 (d, J = 10.1 Hz, 2H), 6.29 (d, J = 10.1 Hz, 2H), 5.63 (t, J = 6.5 Hz, 1H), 5.28 (d, J = 6.5 Hz, 2H), 2.72 (s, 1H); 13 C NMR (125 MHz, CDCl 3 ) δ 216.6, 184.2, 163.5, 142.4, 128.7, 87.5, 79.9, 76.9, 76.4, 67.6; HRMS (ESI) m/z calcd for C 12 H 7 3 [M-H] - = , found = ,2,6-Trimethyl-4-oxocyclohexa-2,5-dien-1-yl buta-2,3-dienoate (1p)

90 31% yield, white solid; 1 H NMR (500 MHz, CDCl 3 ) δ 6.06 (s, 2H), 5.64 (t, J = 6.5 Hz, 1H), 5.26 (d, J = 6.5 Hz, 2H), 1.93 (s, 6H), 1.50 (s, 3H); 13 C NMR (125 MHz, CDCl 3 ) δ 216.5, 185.3, 163.6, 159.5, 126.7, 87.1, 79.7, 79.1, 26.3, 17.7; HRMS (ESI) m/z calcd for C 13 H 14 Na 3 [M+Na] + = , found = Methyl-4-oxocyclohexa-2,5-dien-1-yl penta-2,3-dienoate (6a) 21% yield, white solid; 1 H NMR (500 MHz, CDCl 3 ) δ 6.90 (d, J = 10.2 Hz, 2H), 6.22 (dd, J = 10.0, 0.9 Hz, 2H), 5.61 (qd, J = 7.4, 6.3 Hz, 1H), (m, 1H), 1.77 (dd, J = 7.4, 3.2 Hz, 3H), 1.56 (s, 3H); 13 C NMR (125 MHz, CDCl 3 ) δ 213.7, 185.1, 164.7, 149.2, 128.1, 128.1, 90.8, 87.3, 74.5, 26.3, 12.6; HRMS (ESI) m/z calcd for C 12 H 12 Na 3 [M+Na] + = , found = Methyl-4-oxocyclohexa-2,5-dien-1-yl hexa-2,3-dienoate (6b) 19% yield, white solid; 1 H NMR (500 MHz, CDCl 3 ) δ (m, 2H), 6.22 (q, J = 2.8 Hz, 2H), 5.69 (q, J = 6.4 Hz, 1H), (m, 1H), 2.14 (pd, J = 7.3, 3.2 Hz, 2H), 1.56 (s, 3H), 1.06 (t, J = 7.4 Hz, 3H); 13 C NMR (125 MHz, CDCl 3 ) δ 212.9, 185.1, 164.8, 149.2, 149.2, 128.1, 97.6, 88.4, 74.4, 26.3, 20. 8, 13.2; HRMS (ESI) m/z calcd for C 13 H 14 Na 3 [M+Na] + = , found = Methyl-4-oxocyclohexa-2,5-dien-1-yl 5-methylhexa-2,3-dienoate (6c) 15% yield, white solid; 1 H NMR (500 MHz, CDCl 3 ) δ 6.91 (ddd, J = 10.6, 9.0, 3.5 Hz, 2H), (m, 2H), 5.65 (t, J = 6.1 Hz, 1H), 5.57 (dd, J = 6.1, 3.0 Hz, 1H), 2.47 (dqd, J = 13.3, 6.7, 3.0 Hz, 1H), 1.56 (s, 3H), 1.08 (dd, J = 6.7, 0.8 Hz, 6H); 13 C NMR (125 MHz, CDCl 3 ) δ 212.0, 185.1, 164.8, 149.3, 128.1, 128.1, 103.0, 88.8, 74.4, 27.7, 26.3, 22.3, 22.3; HRMS (ESI) m/z calcd for C 14 H 16 Na 3 [M+Na] + = , found =

91 1-Methyl-4-oxocyclohexa-2,5-dien-1-yl octa-2,3-dienoate (6d) 18% yield, pale yellow oil; 1 H NMR (500 MHz, CDCl 3 ) δ 6.90 (ddd, J = 9.6, 7.7, 3.5 Hz, 2H), 6.23 (d, J = 9.7 Hz, 2H), 5.62 (dd, J = 13.3, 7.1 Hz, 1H), 5.52 (dt, J = 6.0, 2.9 Hz, 1H), 2.13 (qd, J = 7.1, 3.0 Hz, 2H), 1.56 (s, 3H), (m, 2H), 1.38 (dt, J = 13.6, 6.7 Hz, 2H), 0.90 (t, J = 7.2 Hz, 3H); 13 C NMR (125 MHz, CDCl 3 ) δ 213.0, 185.1, 164.8, 149.2, 128.1, 95.8, 87.8, 74.4, 30.8, 27.1, 26.3, 22.0, 13.8; HRMS (ESI) m/z calcd for C 15 H 18 Na 3 [M+Na] + = , found = Methyl-4-oxocyclohexa-2,5-dien-1-yl 6-phenylhexa-2,3-dienoate (6e) 15% yield, pale yellow oil; 1 H NMR (500 MHz, CDCl 3 ) δ 7.29 (t, J = 7.5 Hz, 2H), (m, 3H), (m, 2H), 6.24 (dd, J = 9.9, 1.6 Hz, 2H), 5.68 (q, J = 6.8 Hz, 1H), 5.55 (dt, J = 6.0, 2.9 Hz, 1H), (m, 2H), (m, 2H), 1.56 (s, 3H); 13 C NMR (125 MHz, CDCl 3 ) δ 213.0, 185.0, 164.6, 149.2, 140.8, 128.5, 128.4, 128.1, 126.2, 95.2, 88.2, 74.5, 35.1, 29.0, 26.3; HRMS (ESI) m/z calcd for C 19 H 17 3 [M-H] - = , found = Methyl-4-oxocyclohexa-2,5-dien-1-yl 4-cyclohexylbuta-2,3-dienoate (6f) 15% yield, colorless oil; 1 H NMR (500 MHz, CDCl 3 ) δ (m, 2H), 6.21 (dd, J = 10.0, 1.4 Hz, 2H), 5.60 (t, J = 6.1 Hz, 1H), 5.54 (dd, J = 6.1, 3.0 Hz, 1H), (m, 1H), (m, 2H), (m, 2H), 1.61 (dd, J = 9.1, 3.4 Hz, 1H), 1.54 (d, J = 7.2 Hz, 3H), (m, 5H); 13 C NMR (125 MHz, CDCl 3 ) δ 212.4, 185.0, 164.8, 149.3, 128.1, 101.5, 88.5, 74.3, 36.6, 32.7, 32.7, 26.3, 25.9, 25.7, 25.7; HRMS (ESI) m/z calcd for C 17 H 20 Na 3 [M+Na] + = , found = Methyl-4-oxocyclohexa-2,5-dien-1-yl 5,5-dimethylhexa-2,3-dienoate (6g)

92 11% yield, colorless oil; 1 H NMR (500 MHz, CDCl 3 ) δ (m, 2H), 6.22 (dd, J = 10.3, 1.6 Hz, 2H), 5.59 (dd, J = 24.8, 6.0 Hz, 2H), 1.55 (s, 3H), 1.10 (s, 9H); 13 C NMR (125 MHz, CDCl 3 ) δ 211.2, 185.0, 164.7, 149.3, 149.2, 128.1, 128.1, 107.2, 89.3, 74.3, 32.8, 30.0, 26.3; HRMS (ESI) m/z calcd for C 15 H 18 Na 3 [M+Na] + = , found = ptical resolution was carried out by use of a chiral stationary phase column [Chiralpak IA (2.0 cm I.D. 25 cm), hexane/ch 2 Cl 2 = 3:1, flow 8 ml/min, five cycles, fifth cycle: t 2 = min to get optically pure 6g-1. with ee value >99%, t R (major) =12.9 min (Chiralpak IE, λ = 254 nm, 10% i-prh/hexane, flow rate = 1.0 ml/min). 4-xo-[1,1'-biphenyl]-1(4H)-yl 5-methylhexa-2,3-dienoate (6h) 15% yield, pale yellow solid; 1 H NMR (500 MHz, CDCl 3 ) δ (m, 2H), (m, 3H), (m, 1H), (m, 1H), (m, 1H), (m, 1H), 1.12 (ddd, J = 6.8, 3.1, 1.1 Hz, 6H); 13 C NMR (125 MHz, CDCl 3 ) δ 212.1, 185.6, 164.2, 147.8, 147.8, 136.4, 129.0, 128.7, 128.0, 128.0, 125.4, 103.0, , 77.4, 27.8, 22.4, 22.2; HRMS (ESI) m/z calcd for C 19 H 18 Na 3 [M+Na] + = , found = ,2-Dimethyl-4-oxocyclohexa-2,5-dien-1-yl buta-2,3-dienoate (8) 28% yield, white solid; 1 H NMR (500 MHz, CDCl3) δ 6.85 (d, J = 10.1 Hz, 1H), 6.19 (dd, J = 10.1, 1.9 Hz, 1H), (m, 1H), 5.60 (t, J = 6.5 Hz, 1H), 5.23 (d, J = 6.5 Hz, 2H), 1.92 (d, J = 1.3 Hz, 3H), 1.50 (s, 3H); 13 C NMR (125 MHz, CDCl3) δ 216.4, 185.4, 163.8, 158.9, 149.7, 127.7, 126.8, 87.4, 79.6, 76.7, 26.1, 17.7; HRMS (ESI) m/z calcd for C 12 H 12 Na 3 [M+Na] + = , found = Representative procedure of the intramolecular allenoate Rauhut Currier reaction To a flame dried round bottle flask with a magnetic stirring bar at room temperature under N 2 were added allenoate 1 (0.15 mmol) and EtAc (3 ml), followed by the addition of -ICD (1 mol %, 0.5 mg). The resulting mixture was stirred for 24 h. The solvent was removed under reduced pressure and the residue was purified by column chromatography on silica gel to afford annulation adduct 2.

93 Analytical data products 2 (3aS,7aS)-7a-Methyl-3-vinylidene-3a,7a-dihydrobenzofuran-2,5(3H,4H)-dione (2a) White solid, [α] 25 D = +122 (c 1.0, EtAc); 1 H NMR (500 MHz, CDCl 3 ) δ (m, 1H), 6.03 (d, J = 10.3 Hz, 1H), 5.49 (d, J = 6.2 Hz, 2H), (m, 1H), (m, 2H), 1.72 (s, 3H); 13 C NMR (125 MHz, CDCl 3 ) δ 208.2, 194.4, 167.3, 146.4, 128.9, 98.8, 85.0, 80.6, 44.1, 35.9, 23.9; HRMS (ESI) m/z calcd for C 11 H 9 3 [M-H] - = , found = The ee value was 96%, t R (major) = min, t R (minor) = min (Chiralpak IE, λ = 215 nm, 20% i-prh/hexane, flow rate = 1.0 ml/min). (3aS,7aS)-7a-Ethyl-3-vinylidene-3a,7a-dihydrobenzofuran-2,5(3H,4H)-dione (2b) White solid, [α] 25 D = +113 (c 1.0, EtAc); 1 H NMR (500 MHz, CDCl 3 ) δ 6.61 (dd, J = 10.4, 1.7 Hz, 1H), 6.08 (d, J = 10.4 Hz, 1H), 5.48 (dd, J = 6.2, 1.6 Hz, 2H), 3.58 (dtd, J = 6.0, 4.0, 1.8 Hz, 1H), 2.71 (d, J = 4.2 Hz, 2H), (m, 2H), 1.11 (t, J = 7.5 Hz, 3H); 13 C NMR (125 MHz, CDCl 3 ) δ 208.3, , 167.4, 145.6, 129.8, 99.1, 85.0, 83.1, 41.6, 36.4, 30.5, 7.9; HRMS (ESI) m/z calcd for C 12 H 12 Na 3 [M+Na] + = , found = The ee value was 98%, t R (major) = min, t R (minor) = min (Chiralpak IE, λ = 215 nm, 35% i-prh/hexane, flow rate = 1.0 ml/min). (3aS,7aS)-7a-Propyl-3-vinylidene-3a,7a-dihydrobenzofuran-2,5(3H,4H)-dione (2c) Colorless oil, [α] 25 D = +101 (c 0.6, EtAc); 1 H NMR (500 MHz, CDCl 3 ) δ 6.60 (dd, J = 10.4, 1.1 Hz, 1H), 6.05 (d, J = 10.4 Hz, 1H), 5.46 (d, J = 6.2 Hz, 2H), (m, 1H), (m, 2H), (m, 2H), (m, 2H), (t, J = 7.3 Hz, 3H); 13 C NMR (125 MHz, CDCl 3 ) δ 208.3, 194.7, 167.4, 145.8, 129.6, 99.0, 85.0, 82.9, 42.1, 39.8, 36.3, 17.0, 14.3; HRMS (ESI) m/z calcd for C 13 H 14 Na 3 [M+Na] +

94 = , found = The ee value was 96%, t R (minor) = min, t R (major) = min (Chiralpak IA, λ = 215 nm, 5% i-prh/hexane, flow rate = 1.0 ml/min). (3aS, 7aS)-7a-Isopropyl-3-vinylidene-3a,7a-dihydrobenzofuran-2,5(3H,4H)-dione (2d) Colorless oil, [α] 25 D = +83 (c 1.0, EtAc); 1 H NMR (500 MHz, CDCl 3 ) δ 6.61 (dd, J = 10.5, 1.7 Hz, 1H), 6.14 (d, J = 10.5 Hz, 1H), (m, 2H), (m, 1H), (m, 2H), 2.24 (hept, J = 6.9 Hz, 1H), 1.10 (t, J = 6.9 Hz, 6H); 13 C NMR (125 MHz, CDCl 3 ) δ 208.5, 194.9, 167.3, 144.8, 130.7, 99.8, 85.3, 85.1, 39.3, 37.5, 35.8, 17.4, 16.6; HRMS (ESI) m/z calcd for C 13 H 14 Na 3 [M+Na] + = , found = The ee value was 91%, t R (major) = min, t R (minor) = min (Chiralpak IE, λ = 215 nm, 35% i-prh/hexane, flow rate = 1.0 ml/min). (3aS,7aS)-7a-Butyl-3-vinylidene-3a,7a-dihydrobenzofuran-2,5(3H,4H)-dione (2e) Colorless oil, [α] 25 D = +73 (c 1.0, EtAc); 1 H NMR (500 MHz, CDCl 3 ) δ 6.61 (dd, J = 10.4, 1.7 Hz, 1H), 6.08 (d, J = 10.4 Hz, 1H), (m, 2H), (m, 1H), (m, 2H), (m, 1H), (m, 1H), (m, 2H), (m, 2H), 0.95 (t, J = 7.2 Hz, 3H); 13 C NMR (125 MHz, CDCl 3 ) δ 208.3, 194.7, 167.4, 145.9, 129.6, 99.1, 85.0, 82.9, 42.1, 37.4, 36.4, 25.6, 22.9, 13.8; HRMS (ESI) m/z calcd for C 14 H 15 3 [M-H] - = , found = The ee value was 96%, t R (minor) = min, t R (major) = min (Chiralpak IB, λ = 215 nm, 15% i-prh/hexane, flow rate = 1.0 ml/min). (3aS, 7aS)-7a-Benzyl-3-vinylidene-3a,7a-dihydrobenzofuran-2,5(3H,4H)-dione (2f) White solid, [α] 25 D = +39 (c 1.0, EtAc); 1 H NMR (500 MHz, CDCl 3 ) δ (m, 3H), (m, 2H), 6.58 (dt, J = 10.4, 1.5 Hz, 1H), 6.05 (d, J = 10.4 Hz, 1H), (m, 2H), 3.60 (dt, J = 8.2, 6.0 Hz,

95 1H), 3.36 (dd, J = 20.2, 14.1, 2H), (m, 1H), 2.30 (ddd, J = 17.2, 5.8, 1.1 Hz, 1H); 13 C NMR (125 MHz, CDCl 3 ) δ 208.3, 194.6, 167.2, 145.5, 133.3, 130.4, 129.8, 128.8, 127.9, 98.8, 85.1, 82.5, 43.4, 41.4, 36.0; HRMS (ESI) m/z calcd for C 17 H 13 3 [M-H] - = , found = The ee value was 94%, t R (major) = min, t R (minor) = min (Chiralpak IE, λ = 215 nm, 35% i-prh/hexane, flow rate = 1.0 ml/min). (3aS,7aS)-7a-Phenethyl-3-vinylidene-3a,7a-dihydrobenzofuran-2,5(3H,4H)-dione (2g) Colorless oil, [α] 25 D = +31 (c 1.0, EtAc); 1 H NMR (500 MHz, CDCl 3 ) δ 7.31 (t, J = 7.4 Hz, 2H), (m, 3H), 6.67 (dd, J = 10.4, 1.8 Hz, 1H), 6.10 (d, J = 10.4 Hz, 1H), (m, 2H), (m, 1H), 2.72 (d, J = 4.2 Hz, 2H), 2.34 (ddd, J = 14.4, 11.2, 6.0 Hz, 1H), 2.24 (ddd, J = 14.4, 11.2, 5.8 Hz, 1H); 13 C NMR (125 MHz, CDCl 3 ) δ 208.4, 194.5, 167.3, 145.3, 140.1, 129.8, 128.8, 128.2, 126.6, 98.8, 85.1, 82.5, 42.2, 39.3, 36.2, 29.8; HRMS (ESI) m/z calcd for C 18 H 15 3 [M-H] - = , found = The ee value was 94%, t R (minor) = min, t R (major) = min (Chiralpak IE, λ = 215 nm, 35% i-prh/hexane, flow rate = 1.0 ml/min). Methyl 3-((3aS,7aS)-2,5-dioxo-3-vinylidene-3,3a,4,5-tetrahydrobenzofuran-7a(2H)-yl)propanoate (2h) Colorless oil, [α] 25 D = +72 (c 1.0, EtAc); 1 H NMR (500 MHz, CDCl 3 ) δ 6.57 (dd, J = 10.4, 1.8 Hz, 1H), 6.07 (d, J = 10.4 Hz, 1H), 5.49 (d, J = 6.2 Hz, 2H), 3.69 (s, 3H), (m, 1H), (m, 2H), (m, 2H), (m, 2H); 13 C NMR (125 MHz, CDCl 3 ) δ 208.4, 194.3, 172.6, 166.9, 144.7, 130.0, 98.6, 85.2, 81.8, 52.1, 42.0, 35.9, 31.9, 28.1; HRMS (ESI) m/z calcd for C 14 H 14 Na 5 [M+Na] + = , found = The ee value was 96%, t R (minor) = min, t R (major) = min (Chiralpak IE, λ = 215 nm, 35% i-prh/hexane, flow rate = 1.0 ml/min). (3aS,7aS)-7a-Phenyl-3-vinylidene-3a,7a-dihydrobenzofuran-2,5(3H,4H)-dione (2i)

96 White solid, [α] 25 D = -14 (c 0.7, EtAc); 1 H NMR (500 MHz, CDCl 3 ) δ (m, 5H), 6.73 (dd, J = 10.3, 1.8 Hz, 1H), 6.29 (d, J = 10.3 Hz, 1H), (m, 2H), (m, 1H), 2.81 (dd, J = 17.3, 5.5 Hz, 1H), 2.73 (dd, J = 17.3, 2.6 Hz, 1H); 13 C NMR (125 MHz, CDCl 3 ) δ 208.2, 194.6, 167.1, 144.5, , 130.1, 129.3, 129.3, 124.9, 98.8, 85.2, 83.6, 46.1, 35.5; HRMS (ESI) m/z calcd for C 16 H 11 3 [M-H] - = , found = The ee value was 96%, t R (minor) = min, t R (major) = min (Chiralpak IE, λ = 215 nm, 35% i-prh/hexane, flow rate = 1.0 ml/min). 4-((3aS,7aS)-2,5-Dioxo-3-vinylidene-3,3a,4,5-tetrahydrobenzofuran-7a(2H)-yl)benzonitrile (2j) Pale yellow solid, [α] 25 D = -41 (c 1.0, EtAc); 1 H NMR (500 MHz, CDCl 3 ) δ 7.76 (d, J = 8.3 Hz, 2H), 7.62 (d, J = 8.4 Hz, 2H), 6.67 (dd, J = 10.3, 1.7 Hz, 1H), 6.32 (d, J = 10.3 Hz, 1H), (m, 2H), (m, 1H), (m, 2H); 13 C NMR (125 MHz, CDCl 3 ) δ 208.4, 193.8, 166.4, 143.1, 142.9, 133.1, 130.9, 125.9, 117.9, 113.4, 98.1, 85.6, 82.7, 45.7, 35.4; RMS (ESI) m/z calcd for C 17 H 10 N 3 [M-H] - = , found = The ee value was 96%, t R (minor) = min, t R (major) = min (Chiralpak IE, λ = 215 nm, 35% i-prh/hexane, flow rate = 1.0 ml/min). (3aS,7aS)-7a-(3-Fluorophenyl)-3-vinylidene-3a,7a-dihydrobenzofuran-2,5(3H,4H)-dione (2k) Pale yellow solid, [α] 25 D = -8 (c 1.0, EtAc); 1 H NMR (500 MHz, CDCl 3 ) δ 7.43 (td, J = 8.0, 5.9 Hz, 1H), (m, 2H), 7.12 (td, J = 8.3, 2.5 Hz, 1H), 6.69 (dd, J = 10.3, 1.7 Hz, 1H), 6.29 (d, J = 10.3 Hz, 1H), (m, 2H), (m, 1H), 2.80 (dd, J = 17.4, 5.4 Hz, 1H), 2.73 (dd, J = 17.4, 2.7 Hz, 1H); RMS (ESI) m/z calcd for C 16 H 10 F 3 [M-H] - = , found = ; The ee value was 96%, t R (minor) = 12.6 min, t R (major) = min (Chiralpak IE, λ = 215 nm, 35% i-prh/hexane, flow rate = 1.0 ml/min). (3aS,7aS)-7a-(4-Chlorophenyl)-3-vinylidene-3a,7a-dihydrobenzofuran-2,5(3H,4H)-dione (2l)

Enantioselective Conjugate Addition of 3-Fluoro-Oxindoles to. Vinyl Sulfone: An Organocatalytic Access to Chiral. 3-Fluoro-3-Substituted Oxindoles

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