D. L. Broere, E. Ruijter, Y. Shibata, and K. Tanaka, Synthesis, vol.44, p.323, 2012.

P. E. Berthelot, Hebd. Seances Acad. Sci, vol.1866, p.515

W. Reppe and W. J. Scheweckendiek, Justus Liebigs Ann. Chem, p.104, 1948.

M. Amatore and C. Aubert, Eur. J. Org. Chem, p.265, 2015.

B. R. Galan and T. Rovis, Angew. Chem. Int. Ed, vol.48, p.2830, 2009.

T. Shibata and K. Tsuchikama, Org. Biomol. Chem, 1317.

J. A. Varela and C. J. Saá, Organomet. Chem, vol.694, p.100, 2009.

, D 25 = -1880 (c = 0.14, CHCl3). (Sp,M

H. Nmr, 300 MHz, CDCl3) ? 8.20-8.15 (m, 2H)

, Hz, 1H), 7.82 (d, J = 8.4 Hz, 1H), 7.76-7.68 (m, 3H), 7.60 (d, JH-P = 26.4 Hz, 1H), 7.44-7.30 (m, 4H), 7.16 (t, J = 6.9 Hz, 1H), vol.6

. Hz,

C. Nmr, 75 MHz, CDCl3) ? 141.8 (d, JC-P = 18.7 Hz, C), 138.0 (d, JC-P = 55.3 Hz, C), vol.137

C. H. Hz, J. C. )-;-d, J. C. -p-=-12-;-d, and J. -p-=-;-d, 4 (CH x 2), 129.2 (C), 129.0 (CH), 132.3 (C), 132.1 (d, JC-P = 13.5 Hz, CH), 131.7 (C), 130.8 (C), vol.136, pp.127-133

. Hz, , vol.24

P. Nmr, MHz, CDCl3) ? 24.1

, IR: ?max = 2954, vol.839, pp.695-696, 1455.

, D 25 = -2313 (c = 1, CHCl3)

H. Nmr, CDCl3, 500MHz) ??= 8.12 (d, J = 8.5 Hz, 1H), 8.01 (d, J = 8.0 Hz, 1H), 7.76 (d, J = 7.5 Hz, 2H), 7.53 (d, J = 8.5 Hz, 1H), 7.39-7.29 (m, 5H), 7.23-7.13 (m, 4H), 6.90 (t, J = 8.0 Hz, 1H), 6.59 (d, J = 9.0 Hz, 1H), 5.29 (d, J = 13.0 Hz, 1H), 4.97 (d, J = 13.0 Hz, 1H), 3.00-2.89 (m, 3H), vol.3

P. Nmr, , p.121

, IR: ?max = 2954, vol.695, pp.667-668, 1041.

, ???D 25 = -716 (c = 0.25 in CHCl3). (Sp,M

, Rf = 0.30 (20% EtOAc/petroleum ether)

H. Nmr, CDCl3, 500MHz) ??= 7.71-7.66 (m, 4H), 7.63 (d, J = 8.5 Hz, 1H), 7.52 (d, J = 8.0 Hz, 1H), 7.40-7.32 (m, 5H), 7.28 (d, J = 2.0 Hz, 1H), 7.17-7.13 (m, 2H), vol.7

H. Nmr-(cdcl3, MHz) ??8.92 (d, J = 8.5 Hz, 1H, p.500

, Hz, 1H), 7.98 (d, J = 9.0 Hz, 1H), 7.87-7.77 (m, 4H), 7.75-7.68 (m, 4H), 7.60-7.54 (m, 2H), 7.41-7.32 (m, 3H), 7.17 (t, J = 7.5 Hz, 1H), 6.83 (t, J = 7.5 Hz, 1H), 3.18-3.11 (m, 1H), 1.92-1.86 (m, 1H), 1.83-1.78 (m, 1H), 1.73-1

C. Nmr-(cdcl3, 139.1 (d, J = 54.5 Hz, C), 137.2 (d, J = 9, MHz) ??142.7 (d, J = 16.9 Hz, C), vol.133, p.75

, 130.0 (C), 129.8 (C), 129.7 (C), 129.5 (CH), vol.129, pp.130-137

, 3 (CH), 127.6 (C), vol.128

, CH2), 33.2 (d, J = 11.4 Hz, CH, vol.29

P. Nmr, 121 MHz) ??= 24

, IR: ?max = 2952, pp.664-665, 1029.

, ???D 25 = -1431 (c 1 in CHCl3)

H. Nmr, 300 MHz, CDCl3) ? 8.28 (d, J = 8.4 Hz, 1H), 8.15 (d, J = 8.7 Hz, 1H), 8.09 (dd, J = 8.4, 4.5 Hz, 1H), 8.01 (d, J = 8.1 Hz, 1H), 7.95 (d, J = 8.1 Hz, 1H), 7.82 (d, J = 8.1 Hz, 1H), 7.49 (d, J = 8.7 Hz, 1H), 7.42 (t, J = 8.1 Hz, 1H), 7.35-7.21 (m, 4H), 7.20-7.12 (m, 3H), 6.86 (d, J = 8.7 Hz, 1H), 6.51-6.44 (m, 1H), 6.09 (d, JH-P = 28.2 Hz, 1H)

C. Nmr, 75 Hz, CDCl3) ? 141.4 (d, JC-P = 15.7 Hz, C), 137.7 (d, JC-P = 10.7 Hz, CH), 135.8 (C), 135.5 (d, JC

J. C. P-=-50-;-d, J. C. -p-=-12-;-d, and J. -p-=-2-;-d, , vol.134, pp.127-174

D. and J. 14, 3 (d, JC-P = 10.8 Hz, CH), Hz, CH), vol.126, pp.124-130

P. Nmr, MHz, CDCl3) ? 28

, IR: ?max = 2957, vol.839, pp.695-696, 1218.

, D 25 = +1360 (c = 0.2, CHCl3). (Sp,P)

H. Nmr, 500 MHz, CDCl3) ? 8.23 (d, J = 8.5 Hz, 1H)

, Hz, 1H), 7.64 (d, J = 8.0 Hz, 1H), 7.52 (t, J = 8.0 Hz, 1H), 7.25-7.15 (m, 5H), vol.7

, Hz, 3H), 0.10 (d, J = 7.0 Hz, 3H)

C. Nmr-;-d and J. , 75 MHz, CDCl3) ? 142.4 (d, JC-P = 10.7 Hz, CH), 141.3 (d, JC-P = 15.2 Hz, C), vol.137

C. Hz, J. )-;-d, and . 12, , pp.131-138

D. and J. 13, , vol.128, pp.129-130

C. Hz and J. )-;-d, d, JC-P = 11.1 Hz, CH), 48.2 (CH), 42.2 (d, JC-P = 30.2 Hz, CH, 127.8 (CH), 127.7 (d, JC-P = 8.0 Hz, C), 127.5 (CH x 2), vol.128

P. Nmr, MHz, issue.121

, IR: ?max = 2957, vol.840, pp.696-697, 1087.

, D 25 = +1542 (c = 0.1, CHCl3). (Sp,P)-endo-136a

H. Nmr, CDCl3, 500MHz)???? 8.11 (d, J = 8.0 Hz, 1H), 7.98 (d, J = 8.5 Hz, 1H), 7.71 (d, J = 7.5 Hz, 2H), 7.50 (d, J = 8.0 Hz, 1H), 7.40-7.32 (m, 6H), 7.18-7.15 (m, 3H), 6.88 (t, J = 8.0 Hz, 1H), 6.56 (d, J = 8.5 Hz, 1H), 5.30 (d, J = 13.5 Hz, 1H)

P. Nmr-(cdcl3, MHz) ??25.2. (Rp,P)-exo-136b, p.121

H. Nmr, CDCl3, 500MHz)???? 7.76 (d, J = 8.5 Hz, 1H), 7.73 (d, J = 9.0 Hz, 1H), 7.71 (d, J = 7.0 Hz, 2H), 7.65 (d, J = 8.0 Hz, 1H), 7.59 (d, J = 8.0 Hz, 1H), 7.39-7.31 (m, 4H), vol.7

H. Nmr-(cdcl3, MHz) ??8.97 (d, J = 8.5 Hz, 1H), vol.8, p.500

, Hz, 2H), 8.57 (d, J = 1.5 Hz, 1H), vol.8

, Hz, 1H), 7.84-7.79 (m, 3H), 7.77 (d, J = 8.0 Hz, 2H), 7.63 (d, J = 18.0 Hz, 1H), 7.59 (s, 1H), 7.43-7.34 (m, 4H), 7.18 (t, J = 7.5 Hz, 1H), 6.72 (t, J = 7.5 Hz, 1H), 2.65-2.59 (m, 1H)

. Hz,

C. Nmr-(cdcl3, MHz) ??143.2 (d, J = 15.3 Hz, C), 139.0 (d, J = 53.0 Hz, C), vol.136, pp.130-56

, (C), 129.43 (CH), 129.38 (d, 130.5 (CH), 129.8 (C), vol.24, pp.128-136

, 123.5 (CH), 122.2 (CH), 121.5 (CH), 120.1 (CH), 119.1 (d, J = 6.5 Hz, CH), vol.124

. Hz, 34.0 (d, J = 6.0 Hz, CH2), vol.33

P. Nmr, , pp.121-146

, IR: ?max = 3063, vol.757, pp.687-688, 1042.

, ?? ???D 25 = +1232 (c = 1 in CHCl3). (Rp,P)

H. Nmr-(cdcl3, MHz) ??8.90 (d, J = 9.0 Hz, 1H), 8.88 (d, J = 10.0 Hz, 1H), vol.8, p.500

, Hz, 1H), 6.80 (t, J = 7.5 Hz, 1H), 1.65-1.60 (m, 1H), 1.56-1.50 (m, 1H), 1.28-1.17 (m, 2H)

C. Nmr-(cdcl3, MHz) ??142.2 (d, J = 16.4 Hz, C), 132.2 (C), 132.0 (C), 131.5 (C), 131.2 (bs, CH), 130.8 (C), 130.6 (C), 130.0 (C), vol.128, pp.128-135

, 124.1 (CH), 123.7 (C), 123.5 (CH), vol.124, pp.125-81

P. Nmr, 121 MHz)?? 24.0 (bs)

, ???D 25 = +1372 (c 1 in CHCl3)

H. Nmr, 300 MHz, CDCl3) ? 8.52 (d, J = 8.4 Hz, 1H), 8.23 (d, J = 1.8 Hz, 1H), 8.01 (d, J = 8.4 Hz, 1H), 7.88-7.75 (m, 3H), 7.69 (d, JH-P = 26.1 Hz, 1H)

, Hz, 1H), 3.36-3.05 (m, 8H), 2.10-1.80 (m, 8H), 1.40-1.04 (m, 16H), 0.96-0.80 (m, 6H)

C. Nmr-;-d and J. , 75 MHz, CDCl3) ? 141.5 (d, JC-P = 15.6 Hz, C), 140.0 (C), 138.8 (C), 138.1 (C), vol.137

. Hz, 136.0 (C), 135.2 (C), 135.1 (C), 134.5 (C), 133.8 (d, JC-P = 12.0 Hz, C), pp.131-139

D. , J. C. -p-=-11-;-d, and J. , , vol.126, pp.126-172

. Hz, 122.6 (d, JC-P = 47.4 Hz, C), 120.8 (d, JC-P = 6.5 Hz, CH), 117.6 (CH), 43.5 (CH), vol.39

C. H. Hz and J. )-;-d, 57 (CH2), 34.53 (CH2), JC-P = 5.4 Hz, CH2), vol.35

C. H. Hz and J. )-;-d, Hz, CH), vol.31, issue.2

P. Nmr, MHz, issue.121

, IR: ?max = 2956, vol.708, pp.687-688, 1092.

, D 25 = +1080 (c = 1, CHCl3)

H. Nmr, 500 MHz, CDCl3) ? 8.22 (d, J = 8.0 Hz, 1H), 8.19 (d, J = 8.5 Hz, 1H), 8.15 (d, J = 8.5 Hz, 1H)

, Hz, 1H), 7.57 (d, JH-P = 27.0 Hz, 1H), 7.38 (bs, 2H), 7.27 (d, J = 8.5 Hz, 1H), 7.20 (t, J = 7.0 Hz, 1H), 6.97 (bs, 1H), vol.6

, Hz, 1H), 1.99-1.87 (m, 4H), 1.31-1.24 (m, 8H), 1.18-1.12 (m, 1H), 0.93 (d, J = 6.5 Hz, 3H)

C. Nmr-;-d and J. 11, 132.60 (C), 132.4 (C), 132.2 (d, JC-P = 12.8 Hz, CH), 131.6 (C), 131.5 (CH), 131.0 (CH), 130.5 (C), 129.3 (CH), 129.0 (C), vol.136, p.123

. Hz, 39.7 (d, JC-P = 29.2 Hz, CH), vol.34

. Hz, 32.1 (CH2), 31.6 (CH2), 29.7 (d, JC-P = 9.1 Hz, CH), 24.93 (CH2), 24.88 (d, JC-P = 13.6 Hz, CH2)

P. Nmr, MHz, CDCl3) ? 24

, IR: ?max = 2956, vol.840, pp.692-693, 0912.

, D 25 = +1711 (c = 1, CHCl3)

H. Nmr, 500 MHz, CDCl3) ? 8.47 (d, J = 8.5 Hz, 1H), 8.07 (s, 1H), 7.98 (d, J = 9.0 Hz, 1H), 7.89 (d, J = 9

, Hz, 1H), 7.81 (d, J = 7.5 Hz, 2H), 7.57 (d, J = 26.0 Hz, 1H), 7.39 (t, J = 8.0 Hz, 2H), 7.32 (t, J = 7.0 Hz, 1H)

C. Nmr, 75 Hz, CDCl3) ? 142.7 (C), 141.8 (d, JC-P = 15.3 Hz, C), 140.8 (C), 140.2 (C), 138.8 (C), 138.1 (d, JC-P = 53.4 Hz, C), 137.7 (C), vol.137, pp.135-144

D. and J. 12, JC-P =, vol.12, issue.8, p.133

C. H. Hz, 3 (2xCH), 129.0 (CH), vol.129, p.127

, 3 (2xCH), 124.6 (CH), vol.126

C. H. Hz, J. )-;-d, and . 28, 43.5 (CH), vol.117

, Hz, CH2), 33.6 (CH2), 33.0 (d, JC-P = 11.4 Hz, CH), 31.3 (CH2), 29.8 (d, JC-P = 8.7 Hz, CH), 25.2 (CH2), 24.7 (d, JC-P = 11.4 Hz, CH2), vol.23

P. Nmr, MHz, CDCl3) ? 25 ppm

, D 25 = +1764 (c = 1, CHCl3)

H. Nmr, 500 MHz, CDCl3) ? 8.48 (d, J = 8.5 Hz, 1H), 8.04 (d, J = 2.0 Hz, 1H), 8.04 (d, J = 2.0 Hz, 1H), 7.98 (d, J = 8.5 Hz, 1H), 7.86 (d, J = 9.0 Hz, 1H), 7.82 (d, J = 7.5 Hz, 2H), ), 7.57 (d, J = 26.5 Hz, 1H), 7.39 (t, J = 7.5 Hz, 2H), 7.32 (t, J = 7.5 Hz, 1H), 6.78 (s, 1H), vol.6

C. Nmr, Hz, CDCl3) ? 143.1 (C), 141.8 (d, JC-P = 15.5 Hz, C), 140.6 (C), 140.1 (C), 138.8 (C), vol.138

D. , J. C. -p-=-53-;-d, J. C. -p-=-8-;-d, J. C. -p-=-12-;-d, and J. , 132.0 (C), 131.8 (C), 131.2 (C), 130.4 (C), 130.0 (d, JC-P = 12.8 Hz, CH), vol.129, p.126

, 117.5 (CH), 43.6 (CH), 39.7 (d, JC-P = 29.1 Hz, CH)

D. and J. , Hz, CH2), 33.6 (CH2), 33.0 (d, JC-P = 11.4 Hz, CH), 31.8 (CH2), vol.29

P. Nmr, MHz, issue.121, p.25

, D 25 = +1779 (c = 1, CHCl3)

H. Nmr, 300 MHz, CDCl3) ? 7.65 (d, J = 8.4 Hz, 2H), 7.30 (d, J = 8.4 Hz, 2H), vol.6

, HPLC Analysis: [CHIRALPAK® IA, 25°C, 1% iPrOH/ n-hexane, 1 mL/min, 220 nm, retention times

H. Nmr, 300 MHz, CDCl3) ? 7.69 (d, J = 8.4 Hz, 2H), 7.35 (d, J = 8.1 Hz, 2H), 7.20-7.08 (m, 3H), 7.04-6.96 (m, 2H), vol.6

. Hz,

, HPLC Analysis: [CHIRALPAK® IC, 25°C, 20% iPrOH/ heptane, 1 mL/min, 2160 nm

H. Nmr, 500 MHz, CDCl3) ? 7.29-7.27 (m, 1H), 7.17-7.12 (m, 2H)

. Chiralpak-®-ia, . 25°c, and . Iproh/-n-heptane, HPLC Analysis

, The HCl salt 149 (400 mg, 2.54 mmol) was dissolved in tBuOH (10 mL) and aldehyde 148 (359 mg, 1.82 mmol) and Et3N (0.36 mL, 2.6 mmol) were added successively. The resultant mixture was stirred at rt overnight

, Then the mixture was quenched with saturated aqueous NaHCO3 solution and extracted with ether. The combined organic layers were washed with brine, dried (MgSO4), filtered, and concentrated to give a crude secondary amine, which was directly used in to next step without purification. The above crude secondary amine was dissolved in CH2Cl2 (10 mL), 54 mmol) was added at 0°C and the stirring was continued for 15 min

, 8 mmol) were added successively. The resultant solution was stirred for 1h, diluted with saturated aqueous NaHCO3 solution, and extracted with CH2Cl2. The combined organic layers were washed with brine, dried (MgSO4), filtered, and concentrated. The residue was purified by flash chromatography

H. Nmr, 500 MHz, CDCl3) ? 7.75 (d, J = 8.0 Hz, 2H), 7.33-7.29 (m, 1H), vol.7

, Was prepared using chiral gold promoted cycloisomerisation procedure. Starting from 150

H. Nmr, 29 (s,1H), 300 MHz, CDCl3) ? 7.74-7.65 (m, 2H), 7.38-7.32 (m, 3H), vol.6

, 10% EtOH/heptane, 1 mL/min, 216 nm, retention times: 38.5 min (major) and 42, HPLC Analysis: [CHIRALPAK® IC, 25°C

. Hz,

C. Nmr-(cdcl3, MHz) ??143.4 (C), 136.63 (C), 136.58 (C), 135.8 (C), vol.134, p.75

, HRMS (ESI) calcd. for C30H33NNaO5S2

, 20% iPrOH/ n-heptane, 1mL/min, 209 nm, retention times: 12.5 min (minor) and 15, HPLC Analysis: [CHIRALPAK ® IB, vol.25

, -methylprop-1-enyl)-4,4 bis(phenylsulfonyl)cyclopentyl)methyl)benzene 156b

H. Nmr-(cdcl3, MHz) ??8.08 (d, J = 8.0 Hz, 2H), 7.91 (d, J = 8.0 Hz, 2H), 7.73 (t, J = 7.5 Hz, 1H), 7.65 (t, J = 7.5 Hz, 1H), 7.60 (t, J = 7.5 Hz, 2H), 7.48 (t, J = 7.5 Hz, 2H), p.500

. Hz,

, Hz, 1H), 2.59-2.48 (m, 2H), 2.30-2.21 (m, 2H, vol.5

C. Nmr-(cdcl3, MHz) ??141.7 (C), 136.78 (C), 136.76 (C), 135.4 (C), 134.5 (CH), vol.134, p.75

, 64.6 (CH2), vol.53

, HRMS (ESI) calcd. for C32H37NNaO5S2 [M+CH3CN+Na] + : 602, p.602, 2011.

, 13% iPrOH/ n-heptane, 1mL/min, 212 nm, retention times: 14.9 min (major) and 16, HPLC Analysis: [CHIRALPAK ® IB, vol.25

C. Nmr-(cdcl3, MHz) ??142.6 (C), 136.8 (C), 136.7 (C), 135.5 (C), 134.5 (CH), vol.134, p.75

, 53.6 (CH), 40.4 (CH), 38.4 (CH2), vol.76

, HRMS (ESI) calcd. for C37H45NNaO5S2

, HPLC Analysis: [CHIRALPAK ® IA, 30°C, 10% iPrOH/n-heptane, 1mL/min, 209 nm, retention times: 7.8 min (minor) and 9

, -methylprop-1-enyl)-4,4-bis(phenylsulfonyl)cyclopentyl)methyl) benzene 156g

H. Nmr, CDCl3, 300MHz) ??8.08 (d, J = 7.5 Hz, 2H), 7.92 (d, J = 7.8 Hz, 2H), 7.71 (t, J = 7.2 Hz, 1H), 7.65-7.57 (m, 3H), 7.48 (t, J = 7.5 Hz, 2H), 7.33-7.24 (m, 3H), 7.11 (d, J = 7.2 Hz, 2H), 5.90-5.75 (m, 1H), 5.26 (d, J = 17.4 Hz, 1H), 5.15 (d, J = 10.5 Hz, 1H)

C. Nmr-(cdcl3, MHz) ??141.1 (C), 136.71 (C), 136.68 (C), 135.4 (C), vol.134, p.75

, 116.4 (CH2), 91.2 (C), 78.8 (CH), vol.69

, HRMS (ESI) calcd. for C33H37NNaO5S2, p.614, 2011.

. Chiralpak-®-ic, 13% iPrOH/ n-heptane, 1mL/min, 227 nm, retention times: 19.8 min (major) and 23, HPLC Analysis, vol.30

, 2-bis(phenylsulfonyl)-4-(propan-2-ylidene)-2,3,3a,4, vol.2

H. Nmr, CDCl3, 300MHz) ??8.10-8.07 (m, 4H), 7.74-7.71 (m, 2H), 7.63-7.59 (m, 4H), 5.81 (d, J = 9.5 Hz, 1H)

. Chiralpak-®-id, 15% iPrOH/ n-heptane, 1mL/min, 211nm, retention times: 21.8 min (major) and 23, HPLC Analysis, vol.30

, Synthesis of phosphahelicene-palladium complexe, p.160

, To a solution of freshly reduced phosphine (Sp,P)-107b (0.029 mmol, p.20

H. Nmr-(cdcl3, 500 MHz)??? 8.62 (d, J = 8.5 Hz, 2H)

, J = 8.0 Hz, 2H), 8.05-8.00 (m, 4H), 7.92-7.87 (m, 4H), 7.74 (d, J = 9.0 Hz, 2H), 7.66 (t, J = 4.0 Hz, 2H), 7.61 (d, J = 7.5 Hz, 4H), 7.54-7.36 (m, 12H), 7.17 (d, J = 9.0 Hz, 2H), 7.10 (s, 1H), 6.86 (t, J = 7.5 Hz, 2H), 6.42 (t, J = 7.5 Hz, 2H), vol.5

. Hz, , p.2

H. Nmr-(cdcl3, MHz) ??7.41-7.39 (m, 2H), 7.36 (t, J = 7.5 Hz, 1H), 7.29 (t, J = 7.2 Hz, 1H), 7.03-7.00 (m, 2H), 6.66 (t, J = 7.5 Hz, 1H), 6.55 (d, J = 7.8 Hz, 1H), vol.7, p.500

. Chiralpak-®-ib, . 25°c, and . Iproh/-n-heptane, HPLC Analysis