Pd/NHC sequentially catalyzed atroposelective synthesis of planar-chiral macrocycles.
Yang, Gongming; Liu, Shangde; Ji, Shujie; Wu, Xingsen; Wang, Jian; Chemical science 15 (2024) 19599–19603; doi:10.1039/d4sc05482b

data_1573055
_publ_section_title
;
 Pd/NHC sequentially catalyzed atroposelective synthesis of planar-chiral
 macrocycles.
;
_journal_issue                   46
_journal_name_full               'Chemical science'
_journal_page_first              19599
_journal_page_last               19603
_journal_paper_doi               10.1039/d4sc05482b
_journal_volume                  15
_journal_year                    2024
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C29 H32 Br N O7 S'
_chemical_formula_sum            'C29 H32 Br N O7 S'
_chemical_formula_weight         618.53
_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     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2024-10-29
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2024-10-30 deposited with the CCDC.	2024-11-04 downloaded from the CCDC.
;
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   9.65444(8)
_cell_length_b                   11.52287(10)
_cell_length_c                   25.33694(19)
_cell_measurement_reflns_used    64371
_cell_measurement_temperature    172.99(10)
_cell_measurement_theta_max      66.5410
_cell_measurement_theta_min      3.8200
_cell_volume                     2818.65(4)
_computing_cell_refinement       'CrysAlisPro 1.171.40.78a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.78a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.78a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement
;
XL, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_computing_structure_solution
;
XS, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      172.99(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_measured_fraction_theta_full 0.9851
_diffrn_measured_fraction_theta_max 0.9914
_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      6.00  65.00   0.50    0.50    --   43.40  55.00 -30.00  118
  2  \w    -46.00  42.00   0.50    0.50    --   43.40  37.00  30.00  176
  3  \w    100.00 128.00   0.50    0.50    --   43.40  55.00 -90.00   56
  4  \w    -46.00  19.00   0.50    0.50    --   43.40  55.00 150.00  130
  5  \w    -45.00  17.00   0.50    0.50    --   43.40  55.00   0.00  124
  6  \w    -46.00   1.00   0.50    0.50    --   43.40  55.00 -30.00   94
  7  \w    -46.00  12.00   0.50    0.50    --   43.40  55.00-150.00  116
  8  \w    -45.00  13.00   0.50    0.50    --   43.40  55.00 -90.00  116
  9  \w    -46.00 132.00   0.50    0.50    --   43.40  55.00  60.00  356
 10  \w    -45.00 132.00   0.50    0.50    --   43.40  37.00 -90.00  354
 11  \w    -45.00  63.00   0.50    0.50    --   43.40  18.00-150.00  216
 12  \w     25.00 103.00   0.50    0.50    --   43.40  55.00 120.00  156
 13  \w    -46.00  21.00   0.50    0.50    --   43.40  55.00 120.00  134
 14  \w     61.00  88.00   0.50    0.50    --   90.00  41.00 -10.35   54
 15  \w      1.00  54.00   0.50    0.50    --   90.00  41.00 -10.35  106
 16  \w     64.00 169.00   0.50    0.50    --   90.00  55.00 100.12  210
 17  \w     72.00 121.00   0.50    0.50    --   90.00  50.00 -98.95   98
 18  \w      1.00  34.00   0.50    0.50    --   90.00  50.00 -98.95   66
 19  \w      1.00  26.00   0.50    0.50    --   90.00  55.00 100.12   50
 20  \w    137.00 162.00   0.50    0.50    --   90.00  55.00-148.12   50
 21  \w      1.00  27.00   0.50    0.50    --   90.00  53.00 -77.50   52
 22  \w    140.00 179.00   0.50    0.50    --   90.00  51.00 124.09   78
 23  \w     32.00 130.00   0.50    0.50    --   90.00  53.00 -77.50  196
 24  \w    135.00 179.00   0.50    0.50    --   90.00  53.00 -77.50   88
 25  \w      1.00  81.00   0.50    0.50    --   90.00  53.00 146.88  160
 26  \w    140.00 165.00   0.50    0.50    --   90.00  53.00 146.88   50
 27  \w      1.00  60.00   0.50    0.50    --   90.00  43.00  -5.58  118
 28  \w     69.00  95.00   0.50    0.50    --   90.00  43.00  -5.58   52
 29  \w      1.00  47.00   0.50    0.50    --   90.00  51.00  23.61   92
 30  \w     54.00  89.00   0.50    0.50    --   90.00  51.00  23.61   70
 31  \w     51.00 151.00   0.50    0.50    --   90.00  52.00-113.75  200
 32  \w     95.00 121.00   0.50    0.50    --   90.00  51.00 124.09   52
 33  \w      2.00  65.00   0.50    0.50    --   90.00  51.00 124.09  126
 34  \w      1.00  32.00   0.50    0.50    --   90.00  52.00-113.75   62
 35  \w    118.00 144.00   0.50    0.50    --   90.00  50.00-157.70   52
 36  \w      1.00  30.00   0.50    0.50    --   90.00  45.00 -78.31   58
 37  \w      1.00 179.00   0.50    0.50    --   90.00  52.00  -1.74  356
 38  \w     39.00 121.00   0.50    0.50    --   90.00  50.00  38.34  164
 39  \w    117.00 161.00   0.50    0.50    --   90.00  45.00 -78.31   88
 40  \w      3.00 119.00   0.50    0.50    --   90.00  53.00 153.85  232
 41  \w      1.00  26.00   0.50    0.50    --   90.00  51.00  13.27   50
 42  \w     68.00 120.00   0.50    0.50    --   90.00  51.00  13.27  104
 43  \w      1.00  51.00   0.50    0.50    --   90.00  51.00  30.43  100
 44  \w      1.00 172.00   0.50    0.50    --   90.00  55.00-129.65  342
 45  \w     46.00 156.00   0.50    0.50    --   90.00  55.00  66.54  220
 46  \w      2.00  28.00   0.50    0.50    --   90.00  50.00  38.34   52
 47  \w      1.00  34.00   0.50    0.50    --   90.00  46.00-180.00   66
 48  \w     53.00 126.00   0.50    0.50    --   90.00  46.00-180.00  146
 49  \w     80.00 105.00   0.50    0.50    --   90.00  55.00 -48.19   50
 50  \w      1.00  41.00   0.50    0.50    --   90.00  55.00  66.54   80
 51  \w      1.00  40.00   0.50    0.50    --   90.00  53.00  48.67   78
 52  \w     50.00 103.00   0.50    0.50    --   90.00  53.00  48.67  106
 53  \w    112.00 175.00   0.50    0.50    --   90.00  53.00  48.67  126
 54  \w      1.00  86.00   0.50    0.50    --   90.00  46.00  90.00  170
 55  \w      1.00  73.00   0.50    0.50    --   90.00  46.00 -60.00  144
 56  \w      2.00  37.00   0.50    0.50    --   90.00  28.00  90.00   70
 57  \w     56.00 178.00   0.50    0.50    --   90.00  28.00  90.00  244
 58  \w    141.00 166.00   0.50    0.50    --   90.00  55.00 -35.50   50
 59  \w     64.00 110.00   0.50    0.50    --   90.00  51.00-164.14   92
 60  \w      5.00  44.00   0.50    0.50    --   90.00  28.00 -90.00   78
 61  \w     51.00  81.00   0.50    0.50    --   90.00  28.00 -90.00   60
 62  \w    114.00 140.00   0.50    0.50    --   90.00  28.00 -90.00   52
 63  \w      7.00  61.00   0.50    0.50    --   90.00   9.00 120.00  108
 64  \w     81.00 125.00   0.50    0.50    --   90.00  18.00-150.00   88
 65  \w     65.00 102.00   0.50    0.50    --   90.00  55.00 -35.50   74
 66  \w      7.00  47.00   0.50    0.50    --   90.00  18.00-150.00   80
 67  \w    112.00 165.00   0.50    0.50    --   90.00   9.00 120.00  106
 68  \w      1.00  56.00   0.50    0.50    --   90.00  46.00 120.00  110
 69  \w    137.00 177.00   0.50    0.50    --   90.00  46.00 120.00   80
 70  \w      1.00  26.00   0.50    0.50    --   90.00  55.00 -35.50   50
 71  \w     39.00 128.00   0.50    0.50    --   90.00  46.00 -30.00  178
 72  \w      1.00  29.00   0.50    0.50    --   90.00  51.00-164.14   56
 73  \w      1.00  56.00   0.50    0.50    --   90.00  55.00 -48.19  110
 74  \w      1.00  56.00   0.50    0.50    --   90.00  50.00-157.70  110
 75  \w     54.00 105.00   0.50    0.50    --   90.00  55.00-148.12  102
 76  \w      1.00  33.00   0.50    0.50    --   90.00  55.00-148.12   64
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC11 (RINC): quarter-chi single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1087778000
_diffrn_orient_matrix_UB_12      0.0340030000
_diffrn_orient_matrix_UB_13      -0.0417250000
_diffrn_orient_matrix_UB_21      -0.0387773000
_diffrn_orient_matrix_UB_22      -0.1077487000
_diffrn_orient_matrix_UB_23      -0.0328034000
_diffrn_orient_matrix_UB_31      -0.1101447000
_diffrn_orient_matrix_UB_32      0.0715112000
_diffrn_orient_matrix_UB_33      -0.0296328000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.1334
_diffrn_reflns_av_unetI/netI     0.0351
_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       30
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            80404
_diffrn_reflns_theta_full        66.74
_diffrn_reflns_theta_max         66.74
_diffrn_reflns_theta_min         3.49
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.079
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.55382
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.78a (Rigaku Oxford Diffraction, 2020)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'metallic colourless'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.458
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       needle
_exptl_crystal_F_000             1280
_exptl_crystal_size_max          0.144
_exptl_crystal_size_mid          0.129
_exptl_crystal_size_min          0.084
_refine_diff_density_max         0.673
_refine_diff_density_min         -0.583
_refine_diff_density_rms         0.101
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   -0.003(18)
_refine_ls_extinction_coef       0.0070(5)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     SHELXL
_refine_ls_goodness_of_fit_ref   1.082
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     355
_refine_ls_number_reflns         4948
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.082
_refine_ls_R_factor_all          0.0448
_refine_ls_R_factor_gt           0.0447
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0783P)^2^+1.5320P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1203
_refine_ls_wR_factor_ref         0.1204
_reflns_number_gt                4930
_reflns_number_total             4948
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            d4sc05482b2.cif
_cod_data_source_block           exp_6622ygmre
_cod_depositor_comments          'Adding full bibliography for 1573055.cif.'
_cod_database_code               1573055
_reflns_odcompleteness_completeness 98.51
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Others
 Fixed Uiso: H24(0.053) H2(0.049) H7(0.042) H1A(0.059) H1B(0.059) H4A(0.053)
 H4B(0.053) H20(0.066) H27(0.049) H28(0.049) H25(0.055) H19(0.064) H10(0.044)
 H29A(0.075) H29B(0.075) H29C(0.075) H14A(0.053) H14B(0.053) H15A(0.052)
 H15B(0.052) H22A(0.076) H22B(0.076) H22C(0.076) H21(0.062) H12A(0.058)
 H12B(0.058) H16A(0.055) H16B(0.055) H17A(0.057) H17B(0.057) H13A(0.066)
 H13B(0.066)
 Fixed X: H24(-0.3884) H2(-0.7625) H7(-0.7331) H1A(-0.5038) H1B(-0.5179) H4A(-
 0.7356) H4B(-0.5965) H20(-1.2188) H27(-0.01) H28(-0.2283) H25(-0.1685) H19(-
 0.9772) H10(-0.3108) H29A(0.0984) H29B(0.145) H29C(0.0848) H14A(-0.6429) H14B(-
 0.6546) H15A(-0.4267) H15B(-0.4258) H22A(-0.9153) H22B(-0.9427) H22C(-0.8532)
 H21(-1.2007) H12A(-0.3648) H12B(-0.4149) H16A(-0.6132) H16B(-0.61) H17A(-
 0.3867) H17B(-0.3977) H13A(-0.4827) H13B(-0.6141)
 Fixed Y: H24(-1.0562) H2(-1.0447) H7(-0.8987) H1A(-0.9685) H1B(-0.99) H4A(-
 0.7426) H4B(-0.7984) H20(-0.8124) H27(-1.2635) H28(-1.3117) H25(-1.0041) H19(-
 0.7597) H10(-1.0569) H29A(-1.0153) H29B(-1.1456) H29C(-1.0903) H14A(-1.2179)
 H14B(-1.3413) H15A(-1.319) H15B(-1.1917) H22A(-0.9838) H22B(-1.0149) H22C(-
 0.9059) H21(-0.9701) H12A(-1.243) H12B(-1.3108) H16A(-1.1457) H16B(-1.2723)
 H17A(-1.2356) H17B(-1.1072) H13A(-1.4097) H13B(-1.3658)
 Fixed Z: H24(0.2907) H2(0.1877) H7(-0.03) H1A(0.1478) H1B(0.2088) H4A(0.1131)
 H4B(0.1335) H20(0.1229) H27(0.2297) H28(0.2005) H25(0.3157) H19(0.0953) H10(-
 0.0768) H29A(0.2784) H29B(0.2781) H29C(0.3298) H14A(-0.0273) H14B(-0.0022)
 H15A(0.0318) H15B(0.01) H22A(-0.0709) H22B(-0.1303) H22C(-0.1158) H21(0.1857)
 H12A(-0.0835) H12B(-0.1335) H16A(0.0661) H16B(0.0886) H17A(0.1233)
 H17B(0.1033) H13A(-0.0603) H13B(-0.0903)
;
_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 4.065
_oxdiff_exptl_absorpt_empirical_full_min 0.152