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_1563355
_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         'C25 H32 N2 O2 S'
_chemical_formula_sum            'C25 H32 N2 O2 S'
_chemical_formula_weight         425.09
_space_group_crystal_system      orthorhombic
_space_group_IT_number           18
_space_group_name_Hall           'P 2 2ab'
_space_group_name_H-M_alt        'P 21 21 2'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2020-07-28
_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            8
_cell_length_a                   24.65475(12)
_cell_length_b                   20.81653(9)
_cell_length_c                   8.55464(4)
_cell_measurement_reflns_used    61773
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      69.4210
_cell_measurement_theta_min      2.7760
_cell_volume                     4390.47(4)
_computing_cell_refinement       'CrysAlisPro 1.171.40.80a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.80a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.80a (Rigaku OD, 2020)'
_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      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.976
_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     19.00  51.00   0.50    0.15    --   43.35  38.00   0.00   64
  2  \w     62.00  91.00   0.50    0.15    --   43.35  38.00   0.00   58
  3  \w    111.00 136.00   0.50    0.61    --   97.59 119.00 -49.00   50
  4  \w    142.00 173.00   0.50    0.61    --   97.59 125.00   0.00   62
  5  \w     93.00 118.00   0.50    0.61    --   97.59 158.00 104.00   50
  6  \w     85.00 110.00   0.50    0.15    --   43.35 158.00 104.00   50
  7  \w    -48.00 -18.00   0.50    0.15    --  -43.35 -38.00   0.00   60
  8  \w    -69.00 -12.00   0.50    0.15    --  -43.35 -77.00  90.00  114
  9  \w    -78.00 -14.00   0.50    0.15    --  -43.35 -77.00  30.00  128
 10  \w    -61.00 -12.00   0.50    0.15    --  -43.35 -77.00 -90.00   98
 11  \w    -64.00 -12.00   0.50    0.15    --  -43.35 -77.00-150.00  104
 12  \w    -82.00 -57.00   0.50    0.61    --  -90.25 -83.00 -92.05   50
 13  \w    -86.00 -59.00   0.50    0.61    --  -90.25 -77.00 -90.00   54
 14  \w    -87.00 -57.00   0.50    0.61    --  -90.25 -81.00-136.43   60
 15  \w    -83.00 -58.00   0.50    0.61    --  -90.25 -79.00 -60.28   50
 16  \w    -98.00 -57.00   0.50    0.61    --  -90.25 -83.00 -40.72   82
 17  \w    -84.00 -57.00   0.50    0.61    --  -90.25 -83.00  31.43   54
 18  \w    -85.00 -59.00   0.50    0.61    --  -90.25 -78.00 114.32   52
 19  \w    -83.00 -58.00   0.50    0.61    --  -90.25 -79.00 176.49   50
 20  \w    -84.00 -58.00   0.50    0.61    --  -90.25 -80.00 100.79   52
 21  \w    -98.00 -57.00   0.50    0.61    --  -90.25 -81.00  79.73   82
 22  \w    -94.00 -58.00   0.50    0.61    --  -90.25 -79.00  -9.43   72
 23  \w   -107.00 -82.00   0.50    0.15    --  -43.35-158.00  70.00   50
 24  \w   -148.00 -76.00   0.50    0.61    --  -90.25-158.00  70.00  144
 25  \w   -111.00 -12.00   0.50    0.15    --  -43.35 -77.00 -30.00  198
 26  \w     59.00  84.00   0.50    0.15    --   43.35-158.00  70.00   50
 27  \w     83.00 109.00   0.50    0.61    --   97.59-158.00  70.00   52
 28  \w     75.00 105.00   0.50    0.61    --   97.59 -94.00  60.00   60
 29  \w     51.00 111.00   0.50    0.61    --   97.59-125.00 -60.00  120
 30  \w     90.00 115.00   0.50    0.61    --   97.59-125.00-180.00   50
 31  \w     55.00  86.00   0.50    0.61    --   97.59-125.00-180.00   62
 32  \w     34.00 106.00   0.50    0.61    --   97.59-119.00-135.00  144
 33  \w     28.00  80.00   0.50    0.15    --   43.35-119.00-135.00  104
 34  \w     25.00 105.00   0.50    0.61    --   97.59 -77.00 -60.00  160
 35  \w     42.00  70.00   0.50    0.61    --   97.59 -94.00  60.00   56
 36  \w     22.00  88.00   0.50    0.61    --   97.59 -94.00  30.00  132
 37  \w     24.00 102.00   0.50    0.61    --   97.59 -77.00  60.00  156
 38  \w    -86.00  -9.00   0.50    0.15    --  -43.35 119.00 -49.00  154
 39  \w    -80.00 -54.00   0.50    0.61    --  -90.25 119.00 -49.00   52
 40  \w   -109.00 -41.00   0.50    0.15    --  -43.35 158.00 104.00  136
 41  \w   -108.00  -9.00   0.50    0.15    --  -43.35 -19.00 150.00  198
 42  \w   -116.00 -13.00   0.50    0.15    --  -43.35 -77.00 150.00  206
 43  \w   -113.00 -79.00   0.50    0.15    --  -43.35 -77.00  90.00   68
 44  \w   -121.00 -63.00   0.50    0.15    --  -43.35 -38.00   0.00  116
 45  \w   -117.00 -70.00   0.50    0.15    --  -43.35 -77.00 -90.00   94
 46  \w   -122.00 -96.00   0.50    0.61    --  -90.25-119.00-135.00   52
 47  \w   -125.00 -57.00   0.50    0.61    --  -90.25 -83.00 -65.51  136
 48  \w   -122.00 -60.00   0.50    0.61    --  -90.25 -76.00  42.63  124
 49  \w   -130.00-104.00   0.50    0.61    --  -90.25 -83.00 -92.05   52
 50  \w   -152.00 -57.00   0.50    0.61    --  -90.25 -82.00-105.70  190
 51  \w   -151.00 -58.00   0.50    0.61    --  -90.25 -79.00-167.13  186
 52  \w   -163.00-116.00   0.50    0.61    --  -90.25 -79.00  -9.43   94
 53  \w   -155.00 -95.00   0.50    0.61    --  -90.25 -79.00 -60.28  120
 54  \w   -160.00 -59.00   0.50    0.61    --  -90.25 -77.00  60.00  202
 55  \w   -145.00 -60.00   0.50    0.61    --  -90.25 -75.00 163.61  170
 56  \w   -164.00 -57.00   0.50    0.61    --  -90.25 -81.00 134.78  214
 57  \w   -162.00 -58.00   0.50    0.61    --  -90.25 -80.00  13.76  208
 58  \w   -163.00 -59.00   0.50    0.61    --  -90.25 -77.00 -30.00  208
 59  \w   -165.00 -58.00   0.50    0.61    --  -90.25 -80.00-151.45  214
 60  \w   -163.00-137.00   0.50    0.61    --  -90.25 -83.00 -40.72   52
 61  \w   -165.00 -59.00   0.50    0.61    --  -90.25 -77.00   0.00  212
 62  \w   -162.00-100.00   0.50    0.61    --  -90.25 -79.00 176.49  124
 63  \w   -165.00 -57.00   0.50    0.61    --  -90.25 -83.00  95.01  216
 64  \w   -145.00 -57.00   0.50    0.61    --  -90.25 -81.00-117.67  176
 65  \w   -165.00-115.00   0.50    0.61    --  -90.25 -81.00  79.73  100
 66  \w   -163.00 -59.00   0.50    0.61    --  -90.25 -77.00 150.00  208
 67  \w   -161.00-101.00   0.50    0.61    --  -90.25 -80.00 100.79  120
;
_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      -0.0027097000
_diffrn_orient_matrix_UB_12      0.0732171000
_diffrn_orient_matrix_UB_13      0.0250441000
_diffrn_orient_matrix_UB_21      -0.0618999000
_diffrn_orient_matrix_UB_22      -0.0018124000
_diffrn_orient_matrix_UB_23      -0.0242871000
_diffrn_orient_matrix_UB_31      -0.0080963000
_diffrn_orient_matrix_UB_32      -0.0105965000
_diffrn_orient_matrix_UB_33      0.1766832000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0585
_diffrn_reflns_av_unetI/netI     0.0219
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.976
_diffrn_reflns_limit_h_max       29
_diffrn_reflns_limit_h_min       -29
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_limit_l_min       -9
_diffrn_reflns_number            101872
_diffrn_reflns_point_group_measured_fraction_full 0.989
_diffrn_reflns_point_group_measured_fraction_max 0.967
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         69.478
_diffrn_reflns_theta_min         2.778
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.493
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.47710
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.80a (Rigaku Oxford Diffraction, 2020)
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    1.286
_exptl_crystal_description       block
_exptl_crystal_F_000             1828
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: hexane and ethyl acetate'
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.173
_refine_diff_density_min         -0.292
_refine_diff_density_rms         0.040
_refine_ls_abs_structure_details
;
 Flack x determined using 3357 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   -0.005(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.983
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     547
_refine_ls_number_reflns         7983
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      0.983
_refine_ls_R_factor_all          0.0277
_refine_ls_R_factor_gt           0.0270
_refine_ls_shift/su_max          0.005
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
;
 w=1/[\s^2^(Fo^2^)+(0.0440P)^2^+1.1100P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0702
_refine_ls_wR_factor_ref         0.0707
_reflns_Friedel_coverage         0.764
_reflns_Friedel_fraction_full    0.984
_reflns_Friedel_fraction_max     0.956
_reflns_number_gt                7804
_reflns_number_total             7983
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc02773e2.cif
_cod_data_source_block           exp_633
_cod_depositor_comments
;

2022-05-30
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_formula_sum            'C50 H65 N4 O4 S2'
_cod_original_formula_weight         850.18
_cod_original_formula_moiety         '2(C25 H32 N2 O2 S)'
_cod_original_formula_units_Z            4
_cod_database_code               1563355
_shelxl_version_number           2013-2
_diffrn_oxdiff_digest_frames
;
01108dda27f94ac336a2a2d8762b43d3b507436ea10
;
_diffrn_oxdiff_digest_hkl
;
01d5d7c6add1a1097f0d2cbc66d8fe42bce901
;
_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:
 C35(H35), C36(H36), C37(H37), C39(H39), C42(H42), C10(H10), C11(H11),
 C15(H15), C16(H16), C17(H17)
2.b Secondary CH2 refined with riding coordinates:
 C33(H33A,H33B), C34(H34A,H34B), C38(H38A,H38B), C40(H40A,H40B), C41(H41A,
 H41B), C8(H8A,H8B), C9(H9A,H9B), C12(H12A,H12B), C13(H13A,H13B), C14(H14A,H14B)
2.c Aromatic/amide H refined with riding coordinates:
 C28(H28), C29(H29), C30(H30), C31(H31), C44(H44), C45(H45), C46(H46),
 C47(H47), C3(H3), C4(H4), C5(H5), C6(H6), C19(H19), C20(H20), C21(H21),
 C22(H22)
2.d Idealised Me refined as rotating group:
 C26(H26A,H26B,H26C), C49(H49A,H49B,H49C), C50(H50A,H50B,H50C), C1(H1A,H1B,
 H1C), C24(H24A,H24B,H24C), C25(H25A,H25B,H25C)
;
_shelx_res_checksum              69767
_shelx_hkl_checksum              82374
_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 1.774
_oxdiff_exptl_absorpt_empirical_full_min 0.557