Copper-catalyzed asymmetric cyclization of alkenyl diynes: method development and new mechanistic insights
Zhu, Xin-Qi; Hong, Pan; Zheng, Yan-Xin; Zhen, Ying-Ying; Hong, Feng-Lin; Lu, Xin; Ye, Long-Wu; Chemical Science  (2021) –; doi:10.1039/D1SC02773E

data_1563354
_publ_section_title
;
 Copper-catalyzed asymmetric cyclization of alkenyl diynes: method
 development and new mechanistic insights
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D1SC02773E
_journal_year                    2021
_chemical_absolute_configuration rm
_chemical_formula_moiety         'C24 H23 N O2 S2'
_chemical_formula_sum            'C24 H23 N O2 S2'
_chemical_formula_weight         421.55
_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             2019-12-11
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2020-11-24 deposited with the CCDC.	2021-06-11 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   5.24790(4)
_cell_length_b                   18.15502(12)
_cell_length_c                   21.35505(16)
_cell_measurement_reflns_used    29499
_cell_measurement_temperature    100(1)
_cell_measurement_theta_max      69.9490
_cell_measurement_theta_min      3.1970
_cell_volume                     2034.62(3)
_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(1)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.979
_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     11.00  37.00   0.50    0.05    --    0.00  92.00  25.00   52
  2  \w    -10.00  22.00   0.50    0.05    --    0.00 -92.00 -87.00   64
  3  \w   -143.00-118.00   0.50    0.12    --  -88.50 -92.00 -87.00   50
  4  \w     23.00  64.00   0.50    0.12    --   94.94 -92.00 -87.00   82
  5  \w     75.00 100.00   0.50    0.12    --   94.94 -92.00 -87.00   50
  6  \w    131.00 156.00   0.50    0.12    --   94.94  92.00  25.00   50
  7  \w    -10.00  15.00   0.50    0.05    --    0.00 -37.00 -90.00   50
  8  \w    -12.00  14.00   0.50    0.05    --    0.00 -19.00  60.00   52
  9  \w    -65.00  16.00   0.50    0.05    --    0.00 -19.00 -30.00  162
 10  \w    -25.00  14.00   0.50    0.05    --    0.00 -57.00-180.00   78
 11  \w    -73.00 -17.00   0.50    0.05    --    0.00 -37.00 -90.00  112
 12  \w    -14.00  18.00   0.50    0.05    --    0.00  57.00  30.00   64
 13  \w     39.00  68.00   0.50    0.05    --    0.00  37.00  90.00   58
 14  \w    -73.00 -35.00   0.50    0.05    --    0.00 -19.00  60.00   76
 15  \w    -14.00  50.00   0.50    0.05    --    0.00  37.00-150.00  128
 16  \w     -9.00  20.00   0.50    0.05    --    0.00  37.00  90.00   58
 17  \w    -31.00  -5.00   0.50    0.05    --    0.00 -77.00 -60.00   52
 18  \w    -24.00  15.00   0.50    0.05    --    0.00 -37.00-180.00   78
 19  \w    -56.00 -22.00   0.50    0.05    --    0.00 -19.00-120.00   68
 20  \w     39.00  64.00   0.50    0.05    --    0.00  57.00  30.00   50
 21  \w    -68.00 -42.00   0.50    0.05    --    0.00 -37.00-180.00   52
 22  \w    -70.00 -45.00   0.50    0.05    --    0.00 -57.00-180.00   50
 23  \w    -19.00  15.00   0.50    0.05    --    0.00 -37.00   0.00   68
 24  \w   -144.00-114.00   0.50    0.12    --  -88.50 -47.00  93.80   60
 25  \w    -97.00 -72.00   0.50    0.12    --  -88.50 -57.00 -60.00   50
 26  \w    -93.00 -67.00   0.50    0.12    --  -88.50 -70.00 -83.27   52
 27  \w   -157.00-131.00   0.50    0.12    --  -88.50 -77.00 150.00   52
 28  \w    -90.00 -64.00   0.50    0.12    --  -88.50 -78.00 -24.08   52
 29  \w    -99.00 -73.00   0.50    0.12    --  -88.50 -37.00 -60.00   52
 30  \w   -138.00-105.00   0.50    0.12    --  -88.50 -57.00 -60.00   66
 31  \w   -155.00-129.00   0.50    0.12    --  -88.50 -57.00-150.00   52
 32  \w    -91.00 -65.00   0.50    0.12    --  -88.50 -77.00 150.00   52
 33  \w   -149.00-123.00   0.50    0.12    --  -88.50 -77.00 -60.00   52
 34  \w    -90.00 -65.00   0.50    0.12    --  -88.50 -77.00 -60.00   50
 35  \w   -100.00 -73.00   0.50    0.12    --  -88.50 -37.00 -30.00   54
 36  \w   -155.00-129.00   0.50    0.12    --  -88.50 -77.00  30.00   52
 37  \w   -159.00-111.00   0.50    0.12    --  -88.50 -78.00  10.10   96
 38  \w    -94.00 -68.00   0.50    0.12    --  -88.50 -70.00-148.12   52
 39  \w    -87.00 -62.00   0.50    0.12    --  -88.50 -83.00  72.73   50
 40  \w   -154.00-128.00   0.50    0.12    --  -88.50 -83.00  72.73   52
 41  \w    -90.00 -65.00   0.50    0.12    --  -88.50 -77.00-120.00   50
 42  \w    -95.00 -69.00   0.50    0.12    --  -88.50 -65.00-113.00   52
 43  \w    -90.00 -65.00   0.50    0.12    --  -88.50 -80.00 -41.83   50
 44  \w    -88.00 -63.00   0.50    0.12    --  -88.50 -81.00 136.99   50
 45  \w   -159.00-105.00   0.50    0.12    --  -88.50 -77.00-120.00  108
 46  \w    -98.00 -73.00   0.50    0.12    --  -88.50 -37.00  47.86   50
 47  \w    -94.00 -69.00   0.50    0.12    --  -88.50 -66.00  67.70   50
 48  \w    -88.00 -63.00   0.50    0.12    --  -88.50 -81.00  21.81   50
 49  \w    -93.00 -68.00   0.50    0.12    --  -88.50 -69.00  -8.12   50
 50  \w    -94.00 -68.00   0.50    0.12    --  -88.50 -68.00 130.33   52
 51  \w    -92.00 -66.00   0.50    0.12    --  -88.50 -73.00-177.86   52
 52  \w    -90.00 -65.00   0.50    0.12    --  -88.50 -76.00  43.95   50
 53  \w    -89.00 -63.00   0.50    0.12    --  -88.50 -80.00 169.71   52
 54  \w   -160.00-116.00   0.50    0.12    --  -88.50 -80.00 169.71   88
 55  \w   -122.00 -75.00   0.50    0.12    --  -88.50 -37.00 120.00   94
 56  \w    -88.00 -63.00   0.50    0.12    --  -88.50 -80.00  73.01   50
 57  \w    -99.00 -74.00   0.50    0.12    --  -88.50 -48.00 -56.72   50
 58  \w   -117.00 -72.00   0.50    0.12    --  -88.50 -57.00-150.00   90
 59  \w   -160.00 -75.00   0.50    0.12    --  -88.50 -32.00 -17.13  170
 60  \w    -90.00 -65.00   0.50    0.12    --  -88.50 -77.00-150.00   50
 61  \w    -90.00 -65.00   0.50    0.12    --  -88.50 -76.00  56.21   50
 62  \w    -89.00 -63.00   0.50    0.12    --  -88.50 -80.00 112.63   52
 63  \w    -87.00 -62.00   0.50    0.12    --  -88.50 -83.00 -75.94   50
 64  \w    -87.00 -62.00   0.50    0.12    --  -88.50 -82.00-154.36   50
 65  \w    -95.00 -70.00   0.50    0.12    --  -88.50 -64.00-148.22   50
 66  \w    -91.00 -66.00   0.50    0.12    --  -88.50 -73.00 -73.17   50
 67  \w    -91.00 -27.00   0.50    0.12    --  -88.50 125.00 150.00  128
 68  \w   -148.00 -73.00   0.50    0.12    --  -88.50 -52.00-120.96  150
 69  \w   -130.00-104.00   0.50    0.12    --  -88.50 -48.00 -56.72   52
 70  \w    -40.00 -15.00   0.50    0.12    --  -88.50  92.00  25.00   50
 71  \w   -134.00 -78.00   0.50    0.12    --  -88.50 -29.00  33.43  112
 72  \w    -79.00 -30.00   0.50    0.12    --  -88.50 125.00-180.00   98
 73  \w    -99.00 -74.00   0.50    0.12    --  -88.50 -57.00-139.35   50
 74  \w    -97.00 -72.00   0.50    0.12    --  -88.50 -58.00 -17.11   50
 75  \w   -102.00 -73.00   0.50    0.12    --  -88.50 -43.00 143.34   58
 76  \w    -90.00 -65.00   0.50    0.12    --  -88.50 -77.00  30.00   50
 77  \w   -108.00 -73.00   0.50    0.12    --  -88.50 -47.00  93.80   70
 78  \w   -156.00-130.00   0.50    0.12    --  -88.50 -75.00-107.77   52
 79  \w    -90.00 -65.00   0.50    0.12    --  -88.50 -75.00-107.77   50
 80  \w    -89.00 -64.00   0.50    0.12    --  -88.50 -78.00  10.10   50
 81  \w    -99.00 -63.00   0.50    0.12    --  -88.50 -81.00 103.09   72
 82  \w    -98.00 -73.00   0.50    0.12    --  -88.50 -47.00  32.37   50
 83  \w   -150.00 -73.00   0.50    0.12    --  -88.50 -44.00 -81.85  154
 84  \w    -98.00 -73.00   0.50    0.12    --  -88.50 -40.00   7.75   50
 85  \w    -94.00 -69.00   0.50    0.12    --  -88.50 -69.00 -19.53   50
 86  \w   -159.00-119.00   0.50    0.12    --  -88.50 -68.00-146.01   80
 87  \w    -93.00 -68.00   0.50    0.12    --  -88.50 -68.00-146.01   50
 88  \w    -91.00 -66.00   0.50    0.12    --  -88.50 -77.00 120.00   50
 89  \w    -90.00 -65.00   0.50    0.12    --  -88.50 -76.00 -42.75   50
 90  \w   -124.00 -74.00   0.50    0.12    --  -88.50 -48.00 -86.74  100
 91  \w    -97.00 -72.00   0.50    0.12    --  -88.50 -51.00 177.27   50
 92  \w    -78.00 -44.00   0.50    0.12    --  -88.50  92.00  25.00   68
 93  \w    -98.00 -73.00   0.50    0.12    --  -88.50 -40.00 149.55   50
 94  \w    -90.00 -65.00   0.50    0.12    --  -88.50 -77.00-180.00   50
 95  \w     32.00 119.00   0.50    0.12    --   94.94 -77.00 -30.00  174
 96  \w     33.00 115.00   0.50    0.12    --   94.94 -77.00 -90.00  164
 97  \w     77.00 105.00   0.50    0.12    --   94.94 -99.00 120.00   56
 98  \w     27.00  72.00   0.50    0.12    --   94.94 -99.00 120.00   90
 99  \w     22.00 112.00   0.50    0.12    --   94.94 -77.00 120.00  180
;
_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      -0.0608926000
_diffrn_orient_matrix_UB_12      0.0493790000
_diffrn_orient_matrix_UB_13      0.0567218000
_diffrn_orient_matrix_UB_21      0.1160754000
_diffrn_orient_matrix_UB_22      0.0666341000
_diffrn_orient_matrix_UB_23      -0.0343952000
_diffrn_orient_matrix_UB_31      -0.2626411000
_diffrn_orient_matrix_UB_32      0.0179992000
_diffrn_orient_matrix_UB_33      -0.0283440000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0560
_diffrn_reflns_av_unetI/netI     0.0201
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.979
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            48123
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.968
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         70.570
_diffrn_reflns_theta_min         3.195
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.535
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.53372
_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    1.376
_exptl_crystal_description       block
_exptl_crystal_F_000             888
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: hexane and ethyl acetate'
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.522
_refine_diff_density_min         -0.318
_refine_diff_density_rms         0.043
_refine_ls_abs_structure_details
;
 Flack x determined using 1505 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   0.000(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.040
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     264
_refine_ls_number_reflns         3781
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.040
_refine_ls_R_factor_all          0.0286
_refine_ls_R_factor_gt           0.0281
_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^)+(0.0400P)^2^+0.9000P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0740
_refine_ls_wR_factor_ref         0.0745
_reflns_Friedel_coverage         0.687
_reflns_Friedel_fraction_full    0.997
_reflns_Friedel_fraction_max     0.954
_reflns_number_gt                3719
_reflns_number_total             3781
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc02773e2.cif
_cod_data_source_block           exp_7549
_cod_database_code               1563354
_shelxl_version_number           2013-2
_reflns_odcompleteness_completeness 99.95
_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:
 C15(H15)
2.b Secondary CH2 refined with riding coordinates:
 C12(H12A,H12B), C13(H13A,H13B), C14(H14A,H14B)
2.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C6(H6), C8(H8), C9(H9), C19(H19), C20(H20), C21(H21),
 C22(H22)
2.d Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C23(H23A,H23B,H23C)
;
_shelx_res_checksum              94863
_shelx_hkl_checksum              73563
_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 1.781
_oxdiff_exptl_absorpt_empirical_full_min 0.396