Supplementary Figure 1. Energy diagram of constitutional isomers 1a, 5a and 2a.

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1 Supplementary Figure 1. Energy diagram of constitutional isomers 1a, 5a and 2a. S1

2 Supplementary Figure 2. 1 H NMR spectrum for 1a. S2

3 Supplementary Figure C NMR spectrum for 1a. S3

4 Supplementary Figure 4. 1 H NMR spectrum for 5a. S4

5 Supplementary Figure C NMR spectrum for 5a. S5

6 Supplementary Figure 6. 1 H NMR spectrum for 2a. S6

7 Supplementary Figure C NMR spectrum for 2a. S7

8 Supplementary Figure 8. 1 H NMR spectrum for 4a. S8

9 Supplementary Figure C NMR spectrum for 4a. S9

10 Supplementary Figure H NMR spectrum for 1b. S10

11 Supplementary Figure C NMR spectrum for 1b. S11

12 Supplementary Figure H NMR spectrum for 5b. S12

13 Supplementary Figure C NMR spectrum for 5b. S13

14 Supplementary Figure H NMR spectrum for 4b. S14

15 Supplementary Figure C NMR spectrum for 4b. S15

16 Supplementary Figure H NMR spectrum for 1c. S16

17 Supplementary Figure C NMR spectrum for 1c. S17

18 Supplementary Figure H NMR spectrum for trans-5c. S18

19 Supplementary Figure C NMR spectrum for trans-5c. S19

20 Supplementary Figure H NMR spectrum for cis-5c. S20

21 Supplementary Figure C NMR spectrum for cis-5c. S21

22 Supplementary Figure H NMR spectrum for anti-4c. S22

23 Supplementary Figure C NMR spectrum for anti-4c. S23

24 Supplementary Figure H NMR spectrum for syn-4c. S24

25 Supplementary Figure C NMR spectrum for syn-4c. S25

26 Supplementary Figure H NMR spectrum for 1d. S26

27 Supplementary Figure C NMR spectrum for 1d. S27

28 Supplementary Figure H NMR spectrum for 5d. S28

29 Supplementary Figure C NMR spectrum for 5d. S29

30 Supplementary Figure H NMR spectrum for 4d. S30

31 Supplementary Figure C NMR spectrum for 4d. S31

32 Supplementary Figure H NMR spectrum for 1e. S32

33 Supplementary Figure C NMR spectrum for 1e. S33

34 Supplementary Figure H NMR spectrum for 5e. S34

35 Supplementary Figure C NMR spectrum for 5e. S35

36 Supplementary Figure H NMR spectrum for 4e. S36

37 Supplementary Figure S C NMR spectrum for 4e. S37

38 Supplementary Figure H NMR spectrum for 1f. S38

39 Supplementary Figure C NMR spectrum for 1f. S39

40 Supplementary Figure H NMR spectrum for 5f. S40

41 Supplementary Figure C NMR spectrum for 5f. S41

42 Supplementary Figure H NMR spectrum for 4f. S42

43 Supplementary Figure C NMR spectrum for 4f. S43

44 Supplementary Figure H NMR spectrum for 1g. S44

45 Supplementary Figure C NMR spectrum for 1g. S45

46 Supplementary Figure H NMR spectrum for 5g. S46

47 Supplementary Figure C NMR spectrum for 5g. S47

48 Supplementary Figure H NMR spectrum for 4g. S48

49 Supplementary Figure C NMR spectrum for 4g. S49

50 Supplementary Figure H NMR spectrum for 1h. S50

51 Supplementary Figure C NMR spectrum for 1h. S51

52 Supplementary Figure H NMR spectrum for 5h. S52

53 Supplementary Figure C NMR spectrum for 5h. S53

54 Supplementary Figure H NMR spectrum for 4h. S54

55 Supplementary Figure C NMR spectrum for 4h. S55

56 Retention time (min) %Area Area ( Vsec) Height ( V) Supplementary Figure 56. HPLC chart for (±)-5a. S56

57 Retention time (min) %Area Area ( Vsec) Height ( V) Supplementary Figure S57. HPLC chart for ( )-5a. S57

58 Retention time (min) %Area Area ( Vsec) Height ( V) Supplementary Figure 58. HPLC chart for (+)-5a. S58

59 Retention time (min) %Area Area ( Vsec) Height ( V) Supplementary Figure 59. HPLC chart for (±)-4a. S59

60 Retention time (min) %Area Area ( Vsec) Height ( V) Supplementary Figure 60. HPLC chart for (+)-4a. S60

Supplementary Methods Materials 1,4-dioxane was distilled from sodium/benzophenone ketyl. Anhydrous DCM and Et 2 O were purchased from Kanto Chemical Co.

61 Supplementary Methods Materials 1,4-dioxane was distilled from sodium/benzophenone ketyl. Anhydrous DCM and Et 2 O were purchased from Kanto Chemical Co. Anhydrous DMF was purchased from Wako Pure Chemical Industries. B1 51, C1 51, G1 52, H , [Rh(OH)(cod)] 2 and Ru(H) 2 (CO)(PPh 3 ) 55 3 were prepared according to the literature procedures. All other commercially available chemical resources were used as received without further purification. Synthesis of 1a A solution of 4-pentenylmagnesium bromide in Et 2 O (1.0 M, 35.0 ml, 35.0 mmol) and triethylamine (5.0 ml, 37.0 mmol) in anhydrous toluene (20 ml) was cooled to 0 C. 6-Methylsalicylate A1 (1.80 g, 10.0 mmol) in anhydrous toluene (4 ml) was added dropwise and the reaction mixture was stirred at room temperature for 12 h. A saturated solution of ammonium chloride (10 ml) was added and the mixture was extracted with AcOEt, washed with water and brine, dried over MgSO 4, and evaporated. The residue was purified by column chromatography on silica gel (hexane:acoet = 10:1) to afford ketone A2 (1.96 g, 9.6 mmol, 96%): 1 H NMR: = 1.85 (tt, J = 7.2, 7.2 Hz, 2H), (m, 2H), 2.56 (s, 3H), 2.94 (t, J = 7.6 Hz, 2H), (m, 2H), 5.80 (ddt, J = 16.8, 10.4, 6.4 Hz, 1H), (m, 1H), 6.82 (dd, J = 8.0, 0.8 Hz, 1H), 7.25 (dd, J = 8.0, 7.6 Hz, 1H), (s, 1H); 13 C NMR: = 23.8, 24.1, 33.1, 43.6, 115.4, 116.2, 122.5, 123.1, 134.0, 137.8, 138.6, 161.5, 208.8; IR (neat): 3337, 2934, 1680, 1464, 1285, 912, 779 cm -1 ; HRMS (m/z): [M+H] + calcd. for C 13 H 17 O 2, ; found, To a stirred solution of A2 (1.96 g, 9.6 mmol) in DMF (30 ml) were added to K 2 CO 3 (1.94 g, 14.0 mmol) and allyl bromide (1.80 g, 15.0 mmol). After stirring the reaction mixture for 2 h at 80 C, water was added and extracted with AcOEt, washed with water and brine, dried over MgSO 4, and evaporated. The residue was purified by column chromatography on silica gel S61

62 (hexane:acoet = 20:1) to afford A3 (2.35 g, 9.5 mmol, 99%): 1 H NMR: = 1.80 (tt, J = 7.2, 7.2 Hz, 2H), (m, 2H), 2.21 (s, 3H), 2.80 (t, J = 7.6 Hz, 2H), 4.53 (ddd, J = 5.2, 1.2, 1.2 Hz, 2H), 4.98 (ddt, J = 10.4, 2.4, 1.2 Hz, 1H), 5.02 (ddt, J = 17.2, 1.6, 1.6 Hz, 1H), 5.25 (ddt, J = 10.4, 1.2, 1.2 Hz, 1H), 5.35 (ddt, J = 17.2, 1.6, 1.6 Hz, 1H), 5.80 (ddt, J = 16.8, 10.0, 6.4 Hz, 1H), 5.99 (ddt, J = 17.2, 10.4, 5.2 Hz, 1H), 6.73 (d, J = 8.4 Hz, 1H), 6.79 (d, J = 7.6 Hz, 1H), 7.18 (dd, J = 8.0, 8.0 Hz, 1H); 13 C NMR: = 18.9, 22.7, 33.1, 43.8, 69.1, 109.5, 115.0, 117.5, 123.0, 129.5, 131.6, 132.8, 135.4, 138.2, 155.0, 207.9; IR (neat): 2928, 1695, 1466, 1259, 991, 912, 775 cm -1 ; HRMS (m/z): [M+H] + calcd. for C 16 H 21 O 2, ; found, To a solution of Grubbs 1 st generation catalyst (24.6 mg, mmol) in anhydrous CH 2 Cl 2 (200 ml) were added A3 (733 mg, 3.0 mmol) at 55 C. After stirring for 6 h, the reaction mixture was concentrated. The residue was purified by column chromatography on silica gel (AcOEt) to afford crude A4, which was subjected to the next hydrogenation reaction without further purification. A mixture of A4 and Pd/C (10 %, 150 mg) in anhydrous THF (15 ml) was stirred under hydrogen atmosphere (1 atm) at room temperature for 3 h. The reaction mixture was filtered through a celite pad and concentrated. The residue was purified by flash column chromatography on silica gel (hexane:acoet = 20:1) to afford 1a (242 mg, 1.11 mmol, 37%): 1 H NMR: = (m, 4H), (m, 4H), 2.23 (s, 3H), (m, 2H), 4.15 (t, J = 5.2 Hz, 2H), 6.77 (d, J = 8.4 Hz, 1H), 6.81 (d, J = 7.6 Hz, 1H), 7.20 (dd, J = 8.0, 8.0 Hz, 1H); 13 C NMR: = 18.7, 24.0, 25.4, 26.6, 27.6, 43.1, 71.4, 111.0, 123.4, 129.7, 132.5, 135.1, 156.4, 209.4; IR (neat): 2928, 1693, 1460, 1259, 1072, 777 cm -1 ; HRMS (m/z): [M+H] + calcd. for C 14 H 19 O 2, ; found, S62

Synthesis of 1b To a stirred solution of 2-(allyloxy)benzaldehyde B1 (1.62 g, 10.0 mmol) in anhydrous THF (30 ml) at 0 C was added 4-pentenylmagnesium bromide in anhydrous Et 2 O (1.0 M, 12.0 ml, 12.

63 Synthesis of 1b To a stirred solution of 2-(allyloxy)benzaldehyde B1 (1.62 g, 10.0 mmol) in anhydrous THF (30 ml) at 0 C was added 4-pentenylmagnesium bromide in anhydrous Et 2 O (1.0 M, 12.0 ml, 12.0 mmol) slowly. After stirring for 2 h at room temperature, saturated NH 4 Cl aq was added at 0 C. The mixture was extracted with Et 2 O, washed with water and brine, dried over Na 2 SO 4, and evaporated to afford crude B2. This compound was used without further purification. To a solution of oxalyl chloride (1.0 ml, 11.7 mmol) in anhydrous CH 2 Cl 2 were added dropwise DMSO (1.1 ml, 15.5 mmol) at -78 C. After stirring for 20 min., a solution of crude B2 in anhydrous CH 2 Cl 2 (10 ml) was added slowly to the mixture. The reaction mixture was stirred for 1 h at -78 C, Et 3 N (7.5 ml) was added by syringe. After stirring at room temperature for 40 min., water was added. The mixture was extracted with CH 2 Cl 2, washed with water and brine, dried over MgSO 4, and evaporated. The residue was purified by flash column chromatography on silica gel (hexane:acoet = 20:1) to afford B3 (1.64 g, 7.13 mmol, 71%): 1 H NMR: = 1.79 (tt, J = 7.2, 7.2 Hz, 2H), (m, 2H), 3.01 (t, J = 7.2 Hz, 2H), 4.62 (dt, J = 5.2, 1.6 Hz, 2H), (m, 1H), 5.02 (ddt, J = 17.2, 1.6, 1.6 Hz, 1H), (m, 1H), 5.42 (ddt, J = 17.2, 1.6, 1.2 Hz, 1H), 5.80 (ddt, J = 16.8, 10.4, 6.4 Hz, 1H), (m, 1H), 6.93 (d, J = 8.4 Hz, 1H), (m, 1H), (m, 1H), 7.65 (dd, J = 8.0, 2.0 Hz, 1H); 13 C NMR: = 23.5, 33.3, 43.1, 69.3, 112.6, 114.9, 118.1, 120.8, 128.9, 130.1, 132.6, 133.0, 138.3, 157.3, 202.8; IR (neat): 2934, 1670, 1595, 1448, 1234, 991, 752 cm -1 ; HRMS (m/z): [M+H] + calcd. for C 15 H 19 O 2, ; found, To a solution of Grubbs 1 st generation catalyst in anhydrous CH 2 Cl 2 (100 ml) were added S63

64 B3 (230 mg, 1.0 mmol) at 50 C. After stirring for 5 h, the reaction mixture was concentrated. The residue was purified by flash column chromatography on silica gel (AcOEt) to afford crude (Z)-2,5,6,7-tetrahydro-8H-benzo[b]oxecin-8-one B4, which was subjected to the next hydrogenation reaction without further purification. A mixture of B4 and Pd/C (10 %, 53.0 mg) in anhydrous THF (10 ml) was stirred under hydrogen atmosphere (1 atm) at room temperature for 3 h. The reaction mixture was filtered through a celite pad and concentrated. The residue was purified by flash column chromatography on silica gel (hexane:acoet = 20:1) to afford B5 (75 mg, 0.37 mmol, 37%): 1 H NMR: = (m, 2H), (m, 6H), 2.78 (t, J = 7.2 Hz, 2H), 4.15 (t, J = 6.4 Hz, 2H), 6.95 (d, J = 8.4 Hz, 1H), (m, 1H), (m, 1H), 7.67 (dd, J = 7.6, 1.6 Hz, 1H); 13 C NMR: = 23.0, 23.6, 27.4, 27.5, 41.3, 70.1, 114.0, 121.1, , , 133.2, 158.3, 203.9; IR (neat): 2926, 1668, 1595, 1450, 1292, 1003, 752 cm -1 ; HRMS (m/z): [M+H] + calcd. for C 13 H 17 O 2, ; found, A mixture containing RuH 2 (CO)(PPh 3 ) 3 (9.2 mg, 1.0 mol, 10 mol %), vinyltrimethylsilane (100 mg, 1.0 mmol), B5 (20.4 mg, 0.10 mmol) in toluene (0.10 ml) was stirred at 135 C for 15 h. After being cooled to room temperature, the reaction mixture was passed through a pad of florisil and eluted with ethyl acetate and evaporated. The residue was purified by preparative thin-layer chromatography on silica gel (hexane:acoet = 10:1) to afford 1b (25.5 mg, mmol, 84%). 1 H NMR: = 0.00 (s, 9H), (m, 2H), (m, 4H), (m, 4H), (m, 2H), (m, 2H), 4.14 (t, J = 5.2 Hz, 2H), 6.75 (d, J = 8.4 Hz, 1H), 6.86 (d, J = 7.6 Hz, 1H), 7.23 (dd, J = 8.0, 8.0 Hz, 1H); 13 C NMR: = 1.9, 19.4, 24.1, 25.3, 26.5, 26.9, 27.7, 43.3, 71.5, 110.7, 121.7, 129.9, 131.8, 143.0, 156.4, 209.2; IR (neat): 2930, 1695, 1456, 1246, 831 cm -1 ; HRMS (m/z): [M+H] + calcd. for C 18 H 29 O 2 Si, ; found, S64

Synthesis of 1c 1c was synthesized from C3 in the same way as 1b from B1. C3: 1 H NMR: = 1.78 (tt, J = 7.6, 7.2 Hz, 2H), 2.07-2.15 (m, 2H), 2.29 (s, 3H), 3.00 (t, J = 7.6 Hz, 2H), 4.59 (ddd, J = 5.

65 Synthesis of 1c 1c was synthesized from C3 in the same way as 1b from B1. C3: 1 H NMR: = 1.78 (tt, J = 7.6, 7.2 Hz, 2H), (m, 2H), 2.29 (s, 3H), 3.00 (t, J = 7.6 Hz, 2H), 4.59 (ddd, J = 5.2, 1.6, 1.6 Hz, 2H), 4.96 (ddt, J = 10.4, 2.0, 1.2 Hz, 1H), 5.02 (ddt, J = 17.2, 2.0, 1.6 Hz, 1H), 5.30 (ddt, J = 10.4, 1.6, 1.2 Hz, 1H), 5.41 (ddt, J = 17.2, 1.6, 1.6 Hz, 1H), 5.80 (ddt, J = 16.8, 10.0, 6.8 Hz, 1H), 6.06 (ddt, J = 17.2, 10.4, 5.2 Hz, 1H), 6.83 (d, J = 8.4 Hz, 1H), 7.21 (dd, J = 8.4, 0.4 Hz, 1H), 7.45 (d, J = 1.6 Hz, 1H); 13 C NMR: = 20.2, 23.6, 33.3, 43.2, 69.4, 112.7, 114.8, 117.9, 128.6, 130.1, 130.4, 132.8, 133.5, 138.3, 155.3, 203.1; IR (neat): 2926, 1670, 1495, 1236, 991, 910, 806 cm -1 ; HRMS (m/z): [M+H] + calcd. for C 16 H 21 O 2, ; found, C5: 1 H NMR: = (m, 2H), (m, 6H), 2.27 (s, 3H), 2.75 (t, J = 6.8 Hz, 2H), 4.08 (t, J = 6.4 Hz, 2H), 6.83 (d, J = 8.0 Hz, 1H), (m, 1H), 7.43 (d, J = 2.0 Hz, 1H); 13 C NMR: = 20.3, 23.1, 23.5, 27.1, 27.4, 41.2, 70.3, 114.3, 129.3, 129.7, 130.5, 133.7, 156.2, 204.0; IR (neat): 2924, 1668, 1607, 1495, 1283, 1248, 812 cm -1 ; HRMS (m/z): [M+H] + calcd. for C 14 H 19 O 2, ; found, c: 1 H NMR: = 0.03 (s, 9H), (m, 2H), (m, 4H), (m, 4H), 2.23 (s, 3H), (m, 2H), (m, 2H), 4.11 (t, J = 5.2 Hz, 2H), 6.67 (d, J = 8.4 Hz, 1H), 7.07 (d, J = 8.0 Hz, 1H); 13 C NMR (CD 3 CN): = -2.0, 18.5, 18.9, 24.88, 24.93, 26.3, 27.4, 28.6, 44.6, 72.7, 112.1, 129.8, 132.5, 133.2, 141.2, 155.5, 210.2; IR (neat): 2932, 1695, 1464, 1246, 833 cm -1 ; HRMS (m/z): [M+H] + calcd. for C 19 H 31 O 2 Si, ; found, S65

Synthesis of 1d A mixture containing Cp*RhCl 2 (3.7 mg, 6.0 mol, 2.0 mol %), styrene (46.8 mg, 0.45 mmol), B5 (61.6 mg, 0.30 mmol), AgSbF 6 (8.3 mg, 24 mol, 8.0 mol %) and Cu(OAc) 2 (108 mg, 0.

66 Synthesis of 1d A mixture containing Cp*RhCl 2 (3.7 mg, 6.0 mol, 2.0 mol %), styrene (46.8 mg, 0.45 mmol), B5 (61.6 mg, 0.30 mmol), AgSbF 6 (8.3 mg, 24 mol, 8.0 mol %) and Cu(OAc) 2 (108 mg, 0.60 mmol) in 1,4-dioxane (1.5 ml) was stirred at 120 C for 13 h. After being cooled to room temperature, the reaction mixture was passed through a pad of florisil and eluted with ethyl acetate and evaporated. The residue was purified by preparative thin-layer chromatography on silica gel (hexane:acoet = 10:1) and GPC to afford D1 (62.8 mg, mmol, 68%): 1 H NMR: = (m, 2H), (m, 6H), (m, 2H), 4.18 (t, J = 5.2 Hz, 2H), (m, 1H), 7.06 (d, J = 16.0 Hz, 1H), 7.10 (d, J = 16.0 Hz, 1H), (m, 5H), (m, 2H); 13 C NMR: = 23.8, 25.4, 26.4, 27.3, 43.8, 71.4, 112.4, 118.3, 124.5, 126.7, 127.9, 128.5, 129.9, 131.6, 131.7, 134.6, 136.8, 156.3, 209.1; IR (neat): 2928, 1693, 1568, 1462, 1252, 691 cm -1 ; HRMS (m/z): [M+H] + calcd. for C 21 H 23 O 2, ; found, A mixture of D1 (62.8 mg, mmol) and Pd/C (10 %, 12.4 mg) in anhydrous THF (5 ml) was stirred under hydrogen atmosphere (1 atm) at room temperature for 2 h. The reaction mixture was filtered through a celite pad and concentrated. The residue was purified by preparative thin-layer chromatography on silica gel (hexane:acoet = 10:1) to afford 1d (60.2 mg, mmol, 96%): 1 H NMR: = (m, 4H), (m, 4H), (m, 2H), (m, 2H), (m, 2H), 4.15 (t, J = 5.2 Hz, 2H), 6.80 (d, J = 7.6 Hz, 1H), 6.84 (d, J = 7.6 Hz, 1H), (m, 6H); 13 C NMR: = 24.2, 25.2, 26.5, 27.8, 35.0, 38.2, 43.0, 71.5, 111.2, 122.6, 125.9, 128.3, 128.5, 129.9, 132.4, 139.2, 141.6, 156.6, 209.2; IR (neat): 2359, 1690, 1456, 1267, 1072, 694 cm -1 ; HRMS (m/z): [M+H] + calcd. for C 21 H 25 O 2, ; found, S66

Synthesis of 1e E2 was synthesized from B5 in the same way as 1d from B5. E1: 1 H NMR: = 1.51-1.84 (m, 8H), 2.61-2.68 (m, 2H), 3.77 (s, 3H), 4.17 (t, J = 5.2 Hz, 2H), 6.37 (d, J = 16.0 Hz, 1H), 6.

67 Synthesis of 1e E2 was synthesized from B5 in the same way as 1d from B5. E1: 1 H NMR: = (m, 8H), (m, 2H), 3.77 (s, 3H), 4.17 (t, J = 5.2 Hz, 2H), 6.37 (d, J = 16.0 Hz, 1H), 6.96 (d, J = 8.0 Hz, 1H), 7.23 (d, J = 8.0 Hz, 1H), 7.34 (dd, J = 8.0, 8.0 Hz, 1H), 7.59 (d, J = 16.0 Hz, 1H); 13 C NMR: = 23.8, 25.3, 26.5, 27.5, 43.6, 51.8, 71.7, 114.9, 119.5, 120.9, 130.3, 132.0, 133.2, 140.9, 156.6, 166.7, 207.9; IR (neat): 2937, 1715, 1456, 1269, 1171, 789 cm -1 ; HRMS (APCI) Calcd for C 17 H 21 O 4 [M+H] , found E2: 1 H NMR: = (m, 4H), (m, 4H), (m, 4H), (m, 2H), 3.65 (s, 3H), 4.14 (t, J = 5.2 Hz, 2H), 6.80 (d, J = 8.0 Hz, 1H), 6.84 (d, J = 7.6 Hz, 1H), 7.25 (dd, J = 8.0, 8.0 Hz, 1H); 13 C NMR: = 24.0, 24.9, 26.4, 27.6, 27.8, 35.6, 42.6, 51.3, 71.3, 111.4, 122.1, 130.1, 132.2, 137.8, 156.5, 172.9, 208.7; IR (neat): 2928, 1734, 1693, 1454, 1261, 1169, 1072 cm -1 ; HRMS (m/z): [M+H] + calcd. for C 17 H 23 O 4, ; found, To a lithium aluminum hydride (68.4 mg, 1.8 mmol) in anhydrous THF (2.0 ml) were added dropwise E2 (186 mg, 0.60 mmol) in anhydrous THF (1.0 ml) at 0 C. After stirring the reaction mixture for 10 h at room temperature, AcOEt and water were added slowly at 0 C. The mixture was extracted with AcOEt, washed with water and brine, dried over Na 2 SO 4, and evaporated. The residue was purified by column chromatography on silica gel (hexane:acoet = 3:1) to afford E3 (137 g, 0.52 mmol, 86%): 1 H NMR: = (m, 2H), (m, 2H), (m, 7H), (m, 1H), (m, 1H), (m, 1H), (m, 2H), (m, 2H), (m, 1H), (m, 1H), 5.46 (dd, J = 8.0, 4.0 Hz, 1H), 6.74 (d, S67

68 J = 8.0 Hz, 1H), 6.80 (d, J = 7.6 Hz, 1H), 7.13 (dd, J = 8.0, 7.6 Hz, 1H); 13 C NMR (CD 3 CN): = 23.6, 27.2, 27.3, 28.1, 29.7, 36.1, 37.3, 62.2, 68.2, 71.9, 112.2, 124.6, 128.4, 132.8, 143.1, 158.0; IR (neat): 3296, 2930, 1452, 1252, 1030, 731 cm -1 ; HRMS (m/z): [M+Na] + calcd. for C 16 H 24 O 3 Na, ; found, To a sodium hydride (60 % in oil dispersion, 28.4 mg, 1.8 mmol) in anhydrous DMF (1.0 ml) were added dropwise E3 (137 mg, 0.52 mmol) in anhydrous DMF (1.0 ml) at 0 C. After stirring for 20 min., BnBr (120 mg, 0.70 mmol) was added to the reaction mixture. The reaction mixture was stirred for 3 h at room temperature, then water was added. The mixture was extracted with AcOEt, washed with water and brine, dried over Na 2 SO 4, and evaporated. The residue was purified by column chromatography on silica gel (hexane:acoet = 10:1) to afford E4 (70 mg, 0.20 mmol, 38%): 1 H NMR: = (m, 12H), (m, 2H), 3.53 (t, J = 6.0 Hz, 2H), 3.89 (br s, 1H), (m, 1H), (m, 1H), 4.51 (d, J = 12.0 Hz, 1H), 4.54 (d, J = 12.0 Hz, 1H), 5.37 (dd, J = 6.4, 3.6 Hz, 1H), 6.77 (d, J = 8.0 Hz, 1H), 6.81 (d, J = 6.8 Hz, 1H), (m, 1H), (m, 5H); 13 C NMR: = 22.8, 27.2, 27.35, 27.44, 29.3, 31.5, 35.6, 69.6, 70.1, 71.5, 72.8, 111.5, 123.4, 127.5, , , 128.3, 130.7, 138.5, 140.7, 157.6; IR (neat): 3422, 2926, 1578, 1452, 1234, 1028, 733 cm -1 ; HRMS (m/z): [M+Na] + calcd. for C 23 H 30 O 3 Na, ; found, To a solution of oxalyl chloride (30.4 mg, 0.24 mmol) in anhydrous CH 2 Cl 2 (1.0 ml) were added dropwise DMSO (21.5 L, 0.30 mmol) at -78 C. After stirring for 20 min., a solution of crude E2 (70.0 mg, 0.20 mmol) in anhydrous CH 2 Cl 2 (1.0 ml) was added slowly to the mixture. The reaction mixture was stirred for 1 h at -78 C, Et 3 N (1.0 ml) was added by syringe. After stirring at room temperature for 40 min., water was added. The mixture was extracted with CH 2 Cl 2, washed with water and brine, dried over MgSO 4, and evaporated. The residue was purified by preparative thin-layer chromatography on silica gel (hexane:acoet = 10:1) to afford 1e (17.4 g, mmol, 87%): 1 H NMR: = (m, 4H), (m, 4H), (m, 2H), (m, 4H), 3.48 (t, J = 6.0 Hz, 2H), 4.14 (t, J = 5.2 Hz, 2H), 4.49 (s, 2H), 6.78 (d, J = 8.4 Hz, 1H), 6.84 (d, J = 7.6 Hz, 1H), (m, 6H); 13 C NMR: = 24.1, 25.3, 26.5, 27.7, 29.2, 31.5, 43.2, 69.5, 71.5, 72.8, 111.1, 122.5, 127.5, 127.7, 128.3, 129.8, 132.5, 138.5, 139.4, 156.4, 209.3; IR (neat): 2928, 1693, 1454, 1261, 1090, 733 cm -1 ; HRMS (m/z): [M+H] + calcd. for C 23 H 29 O 3, ; found, S68

Synthesis of 1f 1f was synthesized from B5 in the same way as 1b from B5. Allyltrimethylsilane was employed instead of vinyl trimethylsilane. 24% yield: 1 H NMR: = -0.04 (s, 9H), 0.45-0.55 (m, 2H), 1.

6 Hz, 1H); 13 C NMR: = -1.7, 16.8, 24.2, 25.3, 26.4, 26.5, 27.8, 36.6, 43.3, 71.5, 110.9, 122.5, 129.7, 132.4, 140.2, 156.4, 209.3; IR (neat): 2928, 1695, 1246, 833 cm -1 ; HRMS (m/z): [M+H] + calcd.

69 Synthesis of 1f 1f was synthesized from B5 in the same way as 1b from B5. Allyltrimethylsilane was employed instead of vinyl trimethylsilane. 24% yield: 1 H NMR: = (s, 9H), (m, 2H), (m, 6H), (m, 4H), 2.51 (t, J = 7.6 Hz, 2H), (m, 2H), 4.14 (t, J = 5.2 Hz, 2H), 6.77 (d, J = 8.0 Hz, 1H), 6.83 (d, J = 8.0 Hz, 1H), 7.23 (dd, J = 8.0, 7.6 Hz, 1H); 13 C NMR: = -1.7, 16.8, 24.2, 25.3, 26.4, 26.5, 27.8, 36.6, 43.3, 71.5, 110.9, 122.5, 129.7, 132.4, 140.2, 156.4, 209.3; IR (neat): 2928, 1695, 1246, 833 cm -1 ; HRMS (m/z): [M+H] + calcd. for C 19 H 31 O 2 Si, ; found, Synthesis of 1g G5 was synthesized from G1 in the same way with B5 from B1. The spectroscopic data of G5 were identical to the reported values. 56 G3: 1 H NMR: = 1.82 (tt, J = 7.2, 7.2 Hz, 2H), (m, 2H), (m, 2H), (m, 4H), (m, 4H), (m, 2H), (m, 2H), 7.38 (ddd, J = 8.0, 8.0, 1.6 Hz, 1H), 7.56 (dd, J = 8.0, 1.6 Hz, 1H); 13 C NMR: = 23.3, 33.1, 33.3, 35.8, 41.2, 114.9, 115.3, 125.8, 128.1, 130.9, 131.1, 138.0, 138.1, 138.6, 141.3, 204.8; IR (neat): 2934, 1684, 993, 908, 752 cm -1 ; HRMS (m/z): [M+H] + calcd. for C 16 H 21 O, ; found, S69

229.1582. A mixture containing RuH 2 (CO)(PPh 3 ) 3 (36.6 mg, 0.040 mmol, 10 mol %), vinyltrimethylsilane (400 mg, 4.0 mmol), G5 (80.8 mg, 0.40 mmol) in mesitylene (0.

70 A mixture containing RuH 2 (CO)(PPh 3 ) 3 (36.6 mg, mmol, 10 mol %), vinyltrimethylsilane (400 mg, 4.0 mmol), G5 (80.8 mg, 0.40 mmol) in mesitylene (0.60 ml) was stirred at 180 C for 11 h. After being cooled to room temperature, the reaction mixture was passed through a pad of florisil, eluted with ethyl acetate and evaporated. The residue was purified by preparative thin-layer chromatography on silica gel (hexane:acoet = 20:1) to afford 1g (105.7 mg, 0.35 mmol, 88%). 1 H NMR (C 6 D 6 ): = (s, 9H), (m, 2H), (m, 2H), (m, 4H), (m, 2H), (m, 2H), (m, 2H), (m, 4H), (m, 2H), 7.09 (dd, J = 7.6, 7.6 Hz, 1H); 13 C NMR: = -1.9, 18.9, 22.5, 22.6, 23.5, 27.9, 28.5, 28.6, 29.6, 45.4, 126.2, 127.7, 129.0, 138.8, 139.5, 142.0, 212.2; IR (neat): 2930, 1684, 1246, 829 cm -1 ; HRMS (m/z): [M+H] + calcd. for C 19 H 31 OSi, ; found, Synthesis of 1h 1h was synthesized from H1 in the same way as 1b from B1. H3: 1 H NMR: = 1.78 (tt, J = 7.2, 7.2 Hz, 2H), (m, 2H), 2.60 (dtdd, J = 6.8, 6.4, 1.2, 1.2 Hz, 2H), 3.01 (t, J = 7.6 Hz, 2H), 4.11 (t, J = 6.4 Hz, 2H), 4.96 (ddt, J = 10.4, 2.4, 1.2 Hz, 1H), 5.02 (ddt, J = 16.8, 1.6, 1.6 Hz, 1H), 5.13 (ddt, J = 10.4, 1.6, 1.6 Hz, 1H), 5.19 (ddt, J = 17.2, 1.6, 1.6 Hz, 1H), 5.81 (ddt, J = 16.8, 10.0, 6.4 Hz, 1H), 5.90 (ddt, J = 16.8, 10.4, 6.8 Hz, 1H), 6.93 (d, J = 8.4 Hz, 1H), 6.98 (ddd, J = 7.2, 7.2, 0.8 Hz, 1H), 7.42 (ddd, J = 8.4, 7.2, 2.0 Hz, 1H), 7.66 (dd, J = 7.6, 2.0 Hz, 1H); 13 C NMR: = 23.5, 33.3, 33.6, 43.3, 67.6, 112.1, 114.8, 117.4, 120.6, 128.7, 130.2, 133.1, 134.3, 138.4, 157.7, 202.9; IR (neat): 2924, 1668, 1595, 1448, S70

71 1238, 901, 750 cm -1 ; HRMS (APCI) Calcd for C 16 H 21 O 2 [M+H] , found H5: 1 H NMR: = (m, 6H), (m, 4H), 2.83 (t, J = 6.4 Hz, 2H), 4.13 (t, J = 5.2 Hz, 2H), 6.89 (d, J = 8.4 Hz, 1H), (m, 1H), (m, 1H), 7.44 (dd, J = 7.6, 2.0 Hz, 1H); 13 C NMR: = 24.3, 24.9, 25.1, 25.8, 26.4, 40.8, 69.6, 112.0, 120.4, 128.5, 131.2, 132.3, 157.3, 207.0; IR (neat): 2928, 1668, 1595, 1447, 1242, 1011, 750 cm -1 ; HRMS (m/z): [M+H] + calcd. for C 14 H 19 O 2, ; found, h: 1 H NMR: = 0.00 (s, 9H), (m, 2H), (m, 6H), (m, 4H), (m, 2H), (m, 2H), 3.98 (t, J = 4.8 Hz, 2H), 6.63 (d, J = 8.4 Hz, 1H), 6.79 (d, J = 7.6 Hz, 1H), 7.20 (dd, J = 8.0, 8.0 Hz, 1H); 13 C NMR: = -1.9, 19.5, 22.7, 23.5, 24.4, 24.9, 26.3, 26.9, 41.5, 68.4, 107.6, 120.5, 129.6, 131.9, 142.2, 155.5, 209.8; IR (neat): 2924, 1697, 1578, 1447, 1254, 831 cm -1 ; HRMS (m/z): [M+H] + calcd. for C 19 H 31 O 2 Si, ; found, S71

72 Computational study All calculations were performed with Gaussian 09 software package 57. The density functional theory (DFT) method with the B3LYP (Becke's three-parameter hybrid functional 58, LYP correlation functional 59 ) functional was utilized to fully optimize all the stationary points on the potential energy surface (PES) without symmetry and geometric constraints, in conjunction with at the 6-31G(d) basis set. Zero-point energy, enthalpy, and Gibbs free energy at K and 1 atm were estimated from the gas-phase studies. Harmonic vibration frequency calculations at the same level were performed to verify all stationary points have no imaginary frequency. Uncorrected and thermal corrected energies of stationary points (Unit: Hartree) Compounds E H G 1a a a E: electronic energy, H: sum of electronic and thermal enthalpies, G: sum of electronic and thermal free energies Cartesian coordinates of optimized structures 1a O C C C C C H H C C C H H H C H H S72

73 5a C H H C H H C C H H H H C H H H O O C C C C C H H C C C H H H C H H C S73

74 H H C C C H H H H C H O H H H H a O C C C C C H H C C C H H H C H H C S74

75 H H C H H C C H H H H C H H H O S75

76 Supplementary References (51) Miege, F., Meyer, C. & Cossy, J. Rhodium-Catalyzed Cycloisomerization Involving Cyclopropenes: Efficient stereoselective synthesis of medium-sized heterocyclic scaffolds. Angew. Chem., Int. Ed. 50, (2011). (52) Watson, I. G., Ritter, S. & Toste, F. D. Asymmetric synthesis of medium-sized rings by intramolecular Au(I)-catalyzed cyclopropanation. J. Am. Chem. Soc. 131, (2009). (53) Denhez, C., Medegan, S., Helion, F., Namy, J.-L., Vasse, J.-L. & Szymoniak, J. Reduction of Cp 2 ZrCl 2 with Mischmetall: A new method for generating an efficient Cp 2 Zr equivalent. Org. Lett. 8, (2006). (54) Uson, R., Oro, L. A. & Cabeza, J. A. Bis( 4-1,5-cyclooctadiene)-di- -hydroxodirhodium. Inorg, Synth. 23, (1985). (55) Ahmad, N., Levison, J. J., Robinson, S. D. & Uttley, M. F. Carbonyldihydridotris(triphenylphosphine)ruthenium(II) (White isomer). Inorg, Synth. 15, (1974). (56) Zhang, T., Huang, X., Xue, J. & Sun, S. Ring expansion reaction of α-sulfonyl cyclic ketones via insertion of arynes into C C: a facile and mild access to medium- and large-sized benzannulated carbocycles. Tetrahedron Lett. 50, (2009). (57) Frisch, M. J., Trucks, G. W., Schlegel, H. B., Scuseria, G. E., Robb, M. A., Cheeseman, J. R., Scalmani, G., Barone, V., Mennucci, B., Petersson, G. A., Nakatsuji, H., Caricato, M., Li, X., Hratchian, H. P., Izmaylov, A. F., Bloino, J., Zheng, G., Sonnenberg, J. L., Hada, M., Ehara, M., Toyota, K., Fukuda, R., Hasegawa, J., Ishida, M., Nakajima, T., Honda, Y., Kitao, O., Nakai, H., Vreven, T., Montgomery, Jr., J. A., Peralta, J. E., Ogliaro, F., Bearpark, M., Heyd, J. J., Brothers, E., Kudin, K. N., Staroverov, V. N., Keith, T., Kobayashi, R., Normand, J., Raghavachari, K., Rendell, A., Burant, J. C., Iyengar, S. S., Tomasi, J., Cossi, M., Rega, N., Millam, J. M., Klene, M., Knox, J. E., Cross, J. B., Bakken, V., Adamo, C., Jaramillo, J., Gomperts, R., Stratmann, R. E., Yazyev, O., Austin, A. J., Cammi, R., Pomelli, C., Ochterski, J. W., Martin, R. L., Morokuma, K., Zakrzewski, V. G., Voth, G. A., Salvador, P., Dannenberg, J. J., Dapprich, S., Daniels, A. D., Farkas, O., Foresman, J. B., Ortiz, J. V., Cioslowski, J. & Fox, D. J. Gaussian 09, Revision C.01, Gaussian, Inc., Wallingford CT, (58) Becke, A. D. Density-functional thermochemistry. III. The role of exact exchange. J. Chem. Phys. 98, (1993). (59) Lee, C., Yang, W. & Parr, R. G. Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. Phys. Rev. B 37, (1988). S76

Group 13 BN dehydrocoupling reagents, similar to transition metal catalysts but with unique reactivity. Part A: NMR Studies

Group 13 BN dehydrocoupling reagents, similar to transition metal catalysts but with unique reactivity. Part A: NMR Studies Part A: NMR Studies ESI 1 11 B NMR spectrum of the 2:1 reaction of i Pr 2 NHBH 3 with Al(NMe 2 ) 3 in d 6 -benzene 24 h later 11 B NMR ESI 2 11 B NMR spectrum of the reaction of t BuNH 2 BH 3 with Al(NMe