Copper-Catalyzed Asymmetric Reaction of Alkenyl Diynes with Styrenes by Formal [3 + 2] Cycloaddition via Cu-Containing All-Carbon 1,3-Dipoles: Access to Chiral Pyrrole-Fused Bridged [2.2.1] Skeletons.
Hong, Feng-Lin; Chen, Yang-Bo; Ye, Si-Han; Zhu, Guang-Yu; Zhu, Xin-Qi; Lu, Xin; Liu, Rai-Shung; Ye, Long-Wu; Journal of the American Chemical Society 142 (2020) 7618–7626; doi:10.1021/jacs.0c01918

data_4134716
_publ_section_title
;
 Copper-Catalyzed Asymmetric Reaction of Alkenyl Diynes with Styrenes by
 Formal [3 + 2] Cycloaddition via Cu-Containing All-Carbon 1,3-Dipoles:
 Access to Chiral Pyrrole-Fused Bridged [2.2.1] Skeletons.
;
_journal_issue                   16
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              7618
_journal_page_last               7626
_journal_paper_doi               10.1021/jacs.0c01918
_journal_volume                  142
_journal_year                    2020
_chemical_absolute_configuration rm
_chemical_formula_moiety         'C32 H31 N O3 S'
_chemical_formula_sum            'C32 H31 N O3 S'
_chemical_formula_weight         509.64
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-12-16
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5337)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   9.98750(10)
_cell_length_b                   11.32410(10)
_cell_length_c                   46.9874(3)
_cell_measurement_reflns_used    74176
_cell_measurement_temperature    100.0(3)
_cell_measurement_theta_max      70.4660
_cell_measurement_theta_min      3.7490
_cell_volume                     5314.25(8)
_computing_cell_refinement       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.0(3)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.977
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
--------------------------------------------------------------------------
  1  \w    -15.00  21.00   0.50    0.20    --    0.00  37.00 -63.00   72
  2  \w     39.00  64.00   0.50    0.20    --    0.00  37.00 -63.00   50
  3  \w     33.00  69.00   0.50    0.20    --    0.00  57.00   0.00   72
  4  \w    -10.00  15.00   0.50    0.20    --    0.00 -37.00 141.00   50
  5  \w    -15.00  31.00   0.50    0.20    --    0.00  19.00 150.00   92
  6  \w    -15.00  16.00   0.50    0.20    --    0.00 -19.00  60.00   62
  7  \w    -11.00  70.00   0.50    0.20    --    0.00  19.00  60.00  162
  8  \w    124.00 164.00   0.50    0.80    --   94.94  37.00 -63.00   80
  9  \w     31.00 113.00   0.50    0.80    --   94.94-125.00   0.00  164
 10  \w     31.00 113.00   0.50    0.80    --   94.94-125.00 150.00  164
 11  \w     22.00 103.00   0.50    0.80    --   94.94 -99.00   0.00  162
 12  \w     23.00 109.00   0.50    0.80    --   94.94 -99.00 150.00  172
 13  \w     21.00 109.00   0.50    0.80    --   94.94 -37.00 141.00  176
 14  \w    -15.00  10.00   0.50    0.20    --    0.00  57.00   0.00   50
 15  \w    -17.00  15.00   0.50    0.20    --    0.00 -37.00 -90.00   64
 16  \w    -34.00  13.00   0.50    0.20    --    0.00 -37.00-150.00   94
 17  \w     -7.00  63.00   0.50    0.20    --    0.00  57.00-150.00  140
 18  \w     22.00 103.00   0.50    0.80    --   94.94 -99.00-150.00  162
 19  \w    -62.00 -20.00   0.50    0.20    --    0.00 -37.00 141.00   84
 20  \w    -75.00 -24.00   0.50    0.20    --    0.00 -19.00  60.00  102
 21  \w    -74.00  14.00   0.50    0.20    --    0.00 -37.00  30.00  176
 22  \w    -74.00 -22.00   0.50    0.80    --  -88.50  37.00 -63.00  104
 23  \w    -91.00 -26.00   0.50    0.80    --  -88.50 125.00  30.00  130
 24  \w    -68.00 -24.00   0.50    0.80    --  -88.50 125.00 -30.00   88
 25  \w    -89.00 -15.00   0.50    0.80    --  -88.50 125.00-120.00  148
 26  \w    -66.00 -39.00   0.50    0.20    --    0.00 165.00  -7.79   54
 27  \w   -155.00 -73.00   0.50    0.80    --  -88.50 -37.00 141.00  164
 28  \w    -90.00 -64.00   0.50    0.80    --  -88.50 -78.00 156.65   52
 29  \w    -89.00 -63.00   0.50    0.80    --  -88.50 -80.00 147.67   52
 30  \w    -91.00 -65.00   0.50    0.80    --  -88.50 -77.00 120.00   52
 31  \w    -89.00 -63.00   0.50    0.80    --  -88.50 -80.00 167.64   52
 32  \w    -87.00 -62.00   0.50    0.80    --  -88.50 -83.00 110.63   50
 33  \w    -91.00 -65.00   0.50    0.80    --  -88.50 -78.00  72.55   52
 34  \w    -92.00 -67.00   0.50    0.80    --  -88.50 -70.00  43.99   50
 35  \w    -90.00 -65.00   0.50    0.80    --  -88.50 -76.00  -4.97   50
 36  \w    -94.00 -68.00   0.50    0.80    --  -88.50 -68.00   2.07   52
 37  \w    -91.00 -65.00   0.50    0.80    --  -88.50 -77.00   0.00   52
 38  \w    -91.00 -65.00   0.50    0.80    --  -88.50 -77.00 -60.00   52
 39  \w    -92.00 -66.00   0.50    0.80    --  -88.50 -74.00 -76.97   52
 40  \w    -93.00 -67.00   0.50    0.80    --  -88.50 -71.00 -76.76   52
 41  \w    -90.00 -65.00   0.50    0.80    --  -88.50 -77.00-120.00   50
 42  \w    -87.00 -62.00   0.50    0.80    --  -88.50 -83.00-164.38   50
 43  \w    -91.00 -65.00   0.50    0.80    --  -88.50 -77.00-150.00   52
 44  \w    -90.00 -64.00   0.50    0.80    --  -88.50 -79.00-138.34   52
 45  \w    -92.00 -66.00   0.50    0.80    --  -88.50 -73.00 -88.91   52
 46  \w    -90.00 -65.00   0.50    0.80    --  -88.50 -77.00 -30.00   50
 47  \w    -89.00 -63.00   0.50    0.80    --  -88.50 -83.00  20.04   52
 48  \w    -89.00 -63.00   0.50    0.80    --  -88.50 -81.00  37.45   52
 49  \w    -94.00 -68.00   0.50    0.80    --  -88.50 -69.00  98.36   52
 50  \w    -91.00 -65.00   0.50    0.80    --  -88.50 -77.00  60.00   52
 51  \w    -93.00 -67.00   0.50    0.80    --  -88.50 -71.00  74.78   52
 52  \w    -87.00 -62.00   0.50    0.80    --  -88.50 -82.00  28.09   50
 53  \w    -90.00 -64.00   0.50    0.80    --  -88.50 -79.00  -6.36   52
 54  \w    -92.00 -62.00   0.50    0.80    --  -88.50 -83.00 -13.28   60
 55  \w    -93.00 -67.00   0.50    0.80    --  -88.50 -71.00 -62.54   52
 56  \w    -87.00 -62.00   0.50    0.80    --  -88.50 -82.00-122.82   50
 57  \w    -91.00 -65.00   0.50    0.80    --  -88.50 -77.00 -90.00   52
 58  \w    -90.00 -65.00   0.50    0.80    --  -88.50 -77.00-101.72   50
 59  \w    -95.00 -69.00   0.50    0.80    --  -88.50 -65.00 -59.31   52
 60  \w    -99.00 -73.00   0.50    0.80    --  -88.50 -43.00 -59.23   52
 61  \w    -87.00 -62.00   0.50    0.80    --  -88.50 -82.00-100.35   50
 62  \w    -90.00 -64.00   0.50    0.80    --  -88.50 -78.00-154.92   52
 63  \w    -99.00 -73.00   0.50    0.80    --  -88.50 -57.00-150.00   52
 64  \w    -96.00 -65.00   0.50    0.80    --  -88.50 -77.00-180.00   62
 65  \w   -108.00 -74.00   0.50    0.80    --  -88.50 -42.00-161.00   68
 66  \w    -97.00 -64.00   0.50    0.80    --  -88.50 -78.00-163.33   66
 67  \w    -99.00 -74.00   0.50    0.80    --  -88.50 -41.00-152.09   50
 68  \w   -100.00 -74.00   0.50    0.80    --  -88.50 -39.00-127.73   52
 69  \w    -97.00 -72.00   0.50    0.80    --  -88.50 -56.00-164.27   50
 70  \w    -98.00 -73.00   0.50    0.80    --  -88.50 -55.00-117.74   50
 71  \w   -128.00 -74.00   0.50    0.80    --  -88.50 -42.00-103.25  108
 72  \w   -143.00-117.00   0.50    0.80    --  -88.50 -77.00-120.00   52
 73  \w   -148.00 -72.00   0.50    0.80    --  -88.50 -51.00-175.49  152
 74  \w   -134.00 -74.00   0.50    0.80    --  -88.50 -35.00 -84.80  120
 75  \w   -112.00 -70.00   0.50    0.80    --  -88.50 -64.00  51.56   84
 76  \w    -87.00 -62.00   0.50    0.80    --  -88.50 -82.00  57.04   50
 77  \w    -93.00 -67.00   0.50    0.80    --  -88.50 -71.00 116.68   52
 78  \w    -92.00 -67.00   0.50    0.80    --  -88.50 -71.00 138.58   50
 79  \w    -90.00 -65.00   0.50    0.80    --  -88.50 -75.00  93.79   50
 80  \w    -90.00 -65.00   0.50    0.80    --  -88.50 -76.00 131.56   50
 81  \w    -90.00 -65.00   0.50    0.80    --  -88.50 -77.00  90.00   50
 82  \w    -87.00 -62.00   0.50    0.80    --  -88.50 -83.00 145.23   50
 83  \w    -88.00 -63.00   0.50    0.80    --  -88.50 -81.00 176.07   50
 84  \w   -101.00 -73.00   0.50    0.80    --  -88.50 -46.00  85.93   56
 85  \w    -99.00 -66.00   0.50    0.80    --  -88.50 -73.00  35.41   66
 86  \w   -121.00 -67.00   0.50    0.80    --  -88.50 -70.00  67.52  108
 87  \w   -129.00 -74.00   0.50    0.80    --  -88.50 -46.00 121.43  110
 88  \w   -154.00-128.00   0.50    0.80    --  -88.50 -76.00  -4.97   52
 89  \w   -156.00-117.00   0.50    0.80    --  -88.50 -64.00  51.56   78
 90  \w   -151.00 -74.00   0.50    0.80    --  -88.50 -51.00  -4.77  154
 91  \w   -150.00-124.00   0.50    0.80    --  -88.50 -78.00-154.92   52
 92  \w   -152.00 -91.00   0.50    0.80    --  -88.50-125.00 -90.00  122
 93  \w   -125.00 -73.00   0.50    0.80    --  -88.50 -43.00 -37.47  104
 94  \w   -152.00-127.00   0.50    0.80    --  -88.50 -82.00  28.09   50
 95  \w   -161.00 -73.00   0.50    0.80    --  -88.50 -37.00  60.00  176
 96  \w    -70.00  11.00   0.50    0.20    --    0.00 -57.00 -90.00  162
 97  \w    -69.00 -33.00   0.50    0.20    --    0.00 -37.00 -90.00   72
 98  \w    -74.00 -36.00   0.50    0.20    --    0.00 -37.00-150.00   76
 99  \w   -157.00-110.00   0.50    0.80    --  -88.50 -77.00-101.72   94
100  \w   -160.00-134.00   0.50    0.80    --  -88.50 -71.00  74.78   52
101  \w   -157.00-131.00   0.50    0.80    --  -88.50 -69.00  98.36   52
102  \w   -158.00-132.00   0.50    0.80    --  -88.50 -83.00 110.63   52
103  \w   -157.00-132.00   0.50    0.80    --  -88.50 -76.00 131.56   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1352350000
_diffrn_orient_matrix_UB_12      0.0417719000
_diffrn_orient_matrix_UB_13      -0.0121463000
_diffrn_orient_matrix_UB_21      0.0308985000
_diffrn_orient_matrix_UB_22      -0.1268895000
_diffrn_orient_matrix_UB_23      -0.0098128000
_diffrn_orient_matrix_UB_31      -0.0674551000
_diffrn_orient_matrix_UB_32      0.0255520000
_diffrn_orient_matrix_UB_33      -0.0288380000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0870
_diffrn_reflns_av_unetI/netI     0.0260
_diffrn_reflns_Laue_measured_fraction_full 0.977
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       55
_diffrn_reflns_limit_l_min       -55
_diffrn_reflns_number            144438
_diffrn_reflns_point_group_measured_fraction_full 0.976
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         66.576
_diffrn_reflns_theta_min         3.763
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.348
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.48612
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.53 (Rigaku Oxford Diffraction, 2019)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.274
_exptl_crystal_description       block
_exptl_crystal_F_000             2160
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.381
_refine_diff_density_min         -0.311
_refine_diff_density_rms         0.039
_refine_ls_abs_structure_details
;
 Flack x determined using 3948 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   0.019(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.049
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     671
_refine_ls_number_reflns         9386
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.049
_refine_ls_R_factor_all          0.0356
_refine_ls_R_factor_gt           0.0348
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
;
 w=1/[\s^2^(Fo^2^)+(0.0371P)^2^+3.1466P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0871
_refine_ls_wR_factor_ref         0.0876
_reflns_Friedel_coverage         0.774
_reflns_Friedel_fraction_full    0.975
_reflns_Friedel_fraction_max     1.000
_reflns_number_gt                9184
_reflns_number_total             9386
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c01918_si_003.cif
_cod_data_source_block           C32NO3SH31
_cod_depositor_comments
'Adding full bibliography for 4134716--4134718.cif.'
_cod_database_code               4134716
_shelxl_version_number           2013-2
_diffrn_oxdiff_ac3_digest_frames
;
01e3102f7abea3ed97c161d2001e27ca4f07952f0d1
;
_diffrn_oxdiff_ac3_digest_hkl
;
01fa3639ec5287a9afc85306ef25e1ce48cc96
;
_reflns_odcompleteness_completeness 99.96
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     63.60
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C41(H41), C14(H14), C19(H19), C47(H47)
2.b Secondary CH2 refined with riding coordinates:
 C12(H12A,H12B), C42(H42A,H42B), C44(H44A,H44B), C17(H17A,H17B), C15(H15A,
 H15B), C46(H46A,H46B), C16(H16A,H16B), C43(H43A,H43B)
2.c Aromatic/amide H refined with riding coordinates:
 C28(H28), C27(H27), C10(H10), C57(H57), C6(H6), C63(H63), C36(H36), C60(H60),
 C39(H39), C59(H59), C30(H30), C56(H56), C38(H38), C21(H21), C25(H25), C22(H22),
  C24(H24), C8(H8), C62(H62), C31(H31), C35(H35), C23(H23), C7(H7), C50(H50),
 C53(H53), C4(H4), C49(H49), C51(H51), C3(H3), C52(H52)
2.d Idealised Me refined as rotating group:
 C32(H32A,H32B,H32C), C64(H64A,H64B,H64C), C1(H1A,H1B,H1C), C33(H33A,H33B,H33C)
;
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 2.810
_oxdiff_exptl_absorpt_empirical_full_min 0.437