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_4134718
_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         'C35 H33 N O3 S'
_chemical_formula_sum            'C35 H33 N O3 S'
_chemical_formula_weight         547.68
_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             2020-03-28
_audit_creation_method
;
Olex2 1.2
(compiled 2016.09.09 svn.r3337 for OlexSys, GUI svn.r5227)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.50560(10)
_cell_length_b                   13.3487(3)
_cell_length_c                   25.1954(5)
_cell_measurement_reflns_used    9234
_cell_measurement_temperature    99.9(9)
_cell_measurement_theta_max      75.4570
_cell_measurement_theta_min      3.7350
_cell_volume                     2860.65(9)
_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      99.9(9)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.976
_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     30.00  57.00   0.50    2.21    --   43.18 -36.00 -65.00   54
  2  \w     32.00 132.00   0.50   12.00    --  109.26 -36.00 -65.00  200
  3  \w    107.00 178.00   0.50   12.00    --  109.26  36.00  91.00  142
  4  \w    139.00 175.00   0.50   12.00    --  109.26 125.00 -30.00   72
  5  \w    100.00 130.00   0.50   12.00    --  109.26 125.00 -30.00   60
  6  \w     92.00 171.00   0.50   12.00    --  109.26 125.00  30.00  158
  7  \w     60.00  98.00   0.50    2.21    --   43.18 178.00-120.00   76
  8  \w     47.00  72.00   0.50    2.21    --   43.18  36.00  91.00   50
  9  \w     31.00 132.00   0.50   12.00    --  109.26 -30.00  90.00  202
 10  \w     67.00 105.00   0.50   12.00    --  109.26 -94.00 120.00   76
 11  \w     57.00 101.00   0.50   12.00    --  109.26 -94.00  60.00   88
 12  \w     36.00  76.00   0.50   12.00    --  109.26 -94.00 -30.00   80
 13  \w     37.00  88.00   0.50   12.00    --  109.26-125.00 150.00  102
 14  \w    -62.00  35.00   0.50    2.21    --  -43.18  36.00  91.00  194
 15  \w    -77.00 -16.00   0.50   12.00    --  -90.25 125.00 120.00  122
 16  \w   -112.00 -80.00   0.50   12.00    --  -90.25  36.00  91.00   64
 17  \w   -121.00 -37.00   0.50    2.21    --  -43.18 -36.00 -65.00  168
 18  \w   -125.00-100.00   0.50   12.00    --  -90.25 -36.00 -65.00   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      0.0811941000
_diffrn_orient_matrix_UB_12      0.1031446000
_diffrn_orient_matrix_UB_13      -0.0007262000
_diffrn_orient_matrix_UB_21      0.0177944000
_diffrn_orient_matrix_UB_22      -0.0073596000
_diffrn_orient_matrix_UB_23      -0.0607387000
_diffrn_orient_matrix_UB_31      -0.1608972000
_diffrn_orient_matrix_UB_32      0.0511956000
_diffrn_orient_matrix_UB_33      -0.0071806000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0730
_diffrn_reflns_av_unetI/netI     0.0642
_diffrn_reflns_Laue_measured_fraction_full 0.976
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       3
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            16295
_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         66.601
_diffrn_reflns_theta_min         3.508
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.290
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.63937
_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    1.272
_exptl_crystal_description       block
_exptl_crystal_F_000             1160
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.692
_refine_diff_density_min         -0.502
_refine_diff_density_rms         0.123
_refine_ls_abs_structure_details
;
 Flack x determined using 1896 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   -0.030(15)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.136
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     365
_refine_ls_number_reflns         5042
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.136
_refine_ls_R_factor_all          0.0665
_refine_ls_R_factor_gt           0.0619
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
;
 w=1/[\s^2^(Fo^2^)+(0.1198P)^2^+0.1765P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1546
_refine_ls_wR_factor_ref         0.1688
_reflns_Friedel_coverage         0.753
_reflns_Friedel_fraction_full    0.975
_reflns_Friedel_fraction_max     0.999
_reflns_number_gt                4688
_reflns_number_total             5042
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c01918_si_004.cif
_cod_data_source_block           exp_8344
_cod_depositor_comments
'Adding full bibliography for 4134716--4134718.cif.'
_cod_database_code               4134718
_shelxl_version_number           2013-2
_reflns_odcompleteness_completeness 99.97
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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:
 C29(H29)
2.b Secondary CH2 refined with riding coordinates:
 C28(H28A,H28B)
2.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C5(H5), C6(H6), C8(H8), C11(H11), C14(H14), C15(H15),
 C16(H16), C22(H22), C23(H23), C25(H25), C26(H26), C31(H31), C32(H32), C33(H33),
  C34(H34), C35(H35)
2.d Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C18(H18A,H18B,H18C), C19(H19A,H19B,H19C), C27(H27A,H27B,H27C)
;
_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 2.086
_oxdiff_exptl_absorpt_empirical_full_min 0.298