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_4134717
_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         'C29 H27 N O3 S'
_chemical_formula_sum            'C29 H27 N O3 S'
_chemical_formula_weight         469.57
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_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                 101.5410(10)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   9.76180(10)
_cell_length_b                   10.06990(10)
_cell_length_c                   12.23020(10)
_cell_measurement_reflns_used    19211
_cell_measurement_temperature    99.8(9)
_cell_measurement_theta_max      70.0720
_cell_measurement_theta_min      3.6880
_cell_volume                     1177.93(2)
_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      99.8(9)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.980
_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     -4.00  22.00   0.50    0.05    --    0.00  97.00 162.00   52
  2  \w   -132.00-106.00   0.50    0.05    --  -88.50 -97.00  54.00   52
  3  \w    111.00 136.00   0.50    0.05    --   94.94  97.00 162.00   50
  4  \w     57.00 108.00   0.50    0.05    --   94.94 -97.00  54.00  102
  5  \w     26.00  54.00   0.50    0.05    --   94.94 -97.00  54.00   56
  6  \w    -14.00  17.00   0.50    0.05    --    0.00  57.00 -30.00   62
  7  \w    -22.00  15.00   0.50    0.05    --    0.00 -37.00  90.00   74
  8  \w    -73.00 -24.00   0.50    0.05    --    0.00 -37.00 -90.00   98
  9  \w    -71.00 -24.00   0.50    0.05    --    0.00 -77.00  30.00   94
 10  \w    -15.00  19.00   0.50    0.05    --    0.00  37.00 -60.00   68
 11  \w    -72.00 -47.00   0.50    0.05    --    0.00 -37.00  90.00   50
 12  \w    -24.00  14.00   0.50    0.05    --    0.00 -19.00  90.00   76
 13  \w    -19.00  15.00   0.50    0.05    --    0.00 -37.00 -90.00   68
 14  \w    -70.00 -42.00   0.50    0.05    --    0.00 -19.00-180.00   56
 15  \w     46.00  71.00   0.50    0.05    --    0.00  37.00 -60.00   50
 16  \w     31.00  73.00   0.50    0.05    --    0.00  57.00 -30.00   84
 17  \w    -71.00 -33.00   0.50    0.05    --    0.00 -37.00 150.00   76
 18  \w    -31.00   9.00   0.50    0.05    --    0.00 -19.00-180.00   80
 19  \w    -18.00  23.00   0.50    0.05    --    0.00 -77.00  30.00   82
 20  \w    -26.00  10.00   0.50    0.05    --    0.00 -37.00 150.00   72
 21  \w     32.00  75.00   0.50    0.05    --    0.00  19.00  90.00   86
 22  \w    -60.00 -34.00   0.50    0.05    --    0.00 -19.00  90.00   52
 23  \w    -95.00 -69.00   0.50    0.05    --  -88.50 -68.00-169.24   52
 24  \w    -91.00 -65.00   0.50    0.05    --  -88.50 -77.00  90.00   52
 25  \w   -154.00-128.00   0.50    0.05    --  -88.50 -78.00  23.63   52
 26  \w   -111.00 -73.00   0.50    0.05    --  -88.50 -53.00  80.57   76
 27  \w   -103.00 -68.00   0.50    0.05    --  -88.50 -69.00 -23.81   70
 28  \w    -99.00 -73.00   0.50    0.05    --  -88.50 -55.00 -65.54   52
 29  \w    -66.00 -15.00   0.50    0.05    --  -88.50  57.00 150.00  102
 30  \w   -154.00-128.00   0.50    0.05    --  -88.50 -77.00 -30.00   52
 31  \w   -130.00 -70.00   0.50    0.05    --  -88.50 -63.00  59.38  120
 32  \w   -157.00 -74.00   0.50    0.05    --  -88.50 -39.00-156.33  166
 33  \w   -154.00-100.00   0.50    0.05    --  -88.50 -68.00-169.24  108
 34  \w    -97.00 -71.00   0.50    0.05    --  -88.50 -64.00  17.29   52
 35  \w   -151.00-113.00   0.50    0.05    --  -88.50 -74.00 -99.82   76
 36  \w    -90.00 -64.00   0.50    0.05    --  -88.50 -79.00 157.92   52
 37  \w    -89.00 -63.00   0.50    0.05    --  -88.50 -80.00  59.25   52
 38  \w   -100.00 -74.00   0.50    0.05    --  -88.50 -35.00   9.81   52
 39  \w    -92.00 -66.00   0.50    0.05    --  -88.50 -73.00-132.45   52
 40  \w    -94.00 -68.00   0.50    0.05    --  -88.50 -70.00-125.33   52
 41  \w    -90.00 -65.00   0.50    0.05    --  -88.50 -77.00-180.00   50
 42  \w   -147.00-103.00   0.50    0.05    --  -88.50 -82.00 129.21   88
 43  \w   -158.00-111.00   0.50    0.05    --  -88.50 -77.00-180.00   94
 44  \w   -157.00-128.00   0.50    0.05    --  -88.50 -53.00  80.57   58
 45  \w    -93.00 -67.00   0.50    0.05    --  -88.50 -71.00 -86.91   52
 46  \w    -88.00 -62.00   0.50    0.05    --  -88.50 -82.00 129.21   52
 47  \w    -89.00 -63.00   0.50    0.05    --  -88.50 -83.00 -91.31   52
 48  \w    -90.00 -65.00   0.50    0.05    --  -88.50 -76.00  39.68   50
 49  \w   -160.00-102.00   0.50    0.05    --  -88.50 -76.00  39.68  116
 50  \w   -112.00 -53.00   0.50    0.05    --  -88.50  77.00   0.00  118
 51  \w   -104.00 -76.00   0.50    0.05    --  -88.50  57.00 150.00   56
 52  \w    -93.00 -67.00   0.50    0.05    --  -88.50 -72.00  -5.86   52
 53  \w   -103.00 -73.00   0.50    0.05    --  -88.50 -37.00 120.00   60
 54  \w   -148.00-122.00   0.50    0.05    --  -88.50 -71.00 -86.91   52
 55  \w   -160.00-126.00   0.50    0.05    --  -88.50 -78.00 137.47   68
 56  \w    -89.00 -64.00   0.50    0.05    --  -88.50 -78.00 137.47   50
 57  \w    -87.00 -62.00   0.50    0.05    --  -88.50 -83.00 109.91   50
 58  \w    -92.00 -67.00   0.50    0.05    --  -88.50 -72.00-146.40   50
 59  \w    -91.00 -66.00   0.50    0.05    --  -88.50 -77.00 -30.00   50
 60  \w    -81.00 -23.00   0.50    0.05    --  -88.50  97.00 162.00  116
 61  \w    -94.00 -69.00   0.50    0.05    --  -88.50 -65.00  -3.33   50
 62  \w   -114.00 -69.00   0.50    0.05    --  -88.50 -66.00 -11.90   90
 63  \w    -96.00 -71.00   0.50    0.05    --  -88.50 -60.00 171.83   50
 64  \w   -151.00 -74.00   0.50    0.05    --  -88.50 -29.00 -74.94  154
 65  \w    -92.00 -67.00   0.50    0.05    --  -88.50 -74.00 159.45   50
 66  \w    -88.00 -63.00   0.50    0.05    --  -88.50 -80.00 -65.93   50
 67  \w    -87.00 -62.00   0.50    0.05    --  -88.50 -82.00  78.89   50
 68  \w    -99.00 -72.00   0.50    0.05    --  -88.50 -57.00 120.00   54
 69  \w   -118.00 -74.00   0.50    0.05    --  -88.50 -57.00  60.00   88
 70  \w   -154.00-128.00   0.50    0.05    --  -88.50 -66.00 -11.90   52
 71  \w   -100.00 -75.00   0.50    0.05    --  -88.50 -50.00 -15.46   50
 72  \w   -127.00 -75.00   0.50    0.05    --  -88.50 -46.00 -99.43  104
 73  \w    -96.00 -71.00   0.50    0.05    --  -88.50 -62.00 -67.57   50
 74  \w    -91.00 -66.00   0.50    0.05    --  -88.50 -74.00 -99.82   50
 75  \w    -89.00 -64.00   0.50    0.05    --  -88.50 -78.00  23.63   50
 76  \w   -159.00-111.00   0.50    0.05    --  -88.50 -79.00 157.92   96
 77  \w    -90.00 -65.00   0.50    0.05    --  -88.50 -77.00-150.00   50
 78  \w    -90.00 -65.00   0.50    0.05    --  -88.50 -77.00 -90.00   50
 79  \w    -90.00 -65.00   0.50    0.05    --  -88.50 -77.00 120.00   50
 80  \w    -94.00 -69.00   0.50    0.05    --  -88.50 -71.00 -60.66   50
 81  \w    -86.00 -29.00   0.50    0.05    --  -88.50 125.00-180.00  114
 82  \w     45.00 109.00   0.50    0.05    --   94.94-125.00  60.00  128
 83  \w     86.00 114.00   0.50    0.05    --   94.94-125.00 -60.00   56
 84  \w     49.00  79.00   0.50    0.05    --   94.94-125.00 -60.00   60
 85  \w     92.00 117.00   0.50    0.05    --   94.94-125.00 150.00   50
 86  \w     33.00  70.00   0.50    0.05    --   94.94-125.00 150.00   74
 87  \w     89.00 114.00   0.50    0.05    --   94.94-125.00-120.00   50
 88  \w     60.00  86.00   0.50    0.05    --   94.94-125.00-120.00   52
;
_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      -0.0055959000
_diffrn_orient_matrix_UB_12      -0.1457466000
_diffrn_orient_matrix_UB_13      -0.0389747000
_diffrn_orient_matrix_UB_21      -0.0262682000
_diffrn_orient_matrix_UB_22      -0.0448297000
_diffrn_orient_matrix_UB_23      0.1144714000
_diffrn_orient_matrix_UB_31      -0.1588072000
_diffrn_orient_matrix_UB_32      0.0125523000
_diffrn_orient_matrix_UB_33      -0.0436372000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0385
_diffrn_reflns_av_unetI/netI     0.0232
_diffrn_reflns_Laue_measured_fraction_full 0.980
_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       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            24444
_diffrn_reflns_point_group_measured_fraction_full 0.978
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         66.590
_diffrn_reflns_theta_min         3.689
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.474
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.53618
_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 black'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.324
_exptl_crystal_description       block
_exptl_crystal_F_000             496
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.221
_refine_diff_density_min         -0.356
_refine_diff_density_rms         0.042
_refine_ls_abs_structure_details
;
 Flack x determined using 1911 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   0.007(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.031
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     309
_refine_ls_number_reflns         4164
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.031
_refine_ls_R_factor_all          0.0272
_refine_ls_R_factor_gt           0.0265
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
;
 w=1/[\s^2^(Fo^2^)+(0.0419P)^2^+0.2316P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0671
_refine_ls_wR_factor_ref         0.0675
_reflns_Friedel_coverage         0.880
_reflns_Friedel_fraction_full    0.975
_reflns_Friedel_fraction_max     0.996
_reflns_number_gt                4129
_reflns_number_total             4164
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c01918_si_002.cif
_cod_data_source_block           C29NO3SH27
_cod_depositor_comments
'Adding full bibliography for 4134716--4134718.cif.'
_cod_database_code               4134717
_shelxl_version_number           2013-2
_diffrn_oxdiff_ac3_digest_frames
;
015ae2f37708c5fe6b6fc81595c0035ebf060361299
;
_diffrn_oxdiff_ac3_digest_hkl
;
01cb072c25000a7c7bdf340c5c4a458133bf6f
;
_reflns_odcompleteness_completeness 100.00
_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:
 C16(H16), C13(H13)
2.b Secondary CH2 refined with riding coordinates:
 C14(H14A,H14B), C12(H12A,H12B)
2.c Aromatic/amide H refined with riding coordinates:
 C11(H11), C24(H24), C25(H25), C6(H6), C19(H19), C5(H5), C2(H2), C28(H28),
 C18(H18), C22(H22), C21(H21), C3(H3), C20(H20), C27(H27), C8(H8)
2.d Idealised Me refined as rotating group:
 C29(H29A,H29B,H29C), C7(H7A,H7B,H7C)
;
_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 1.890
_oxdiff_exptl_absorpt_empirical_full_min 0.497