Palladium/XuPhos-catalyzed enantioselective cascade Heck/intermolecular C(sp<sup>2</sup>)-H alkylation reaction.
Fang, Chao; Wang, Quan-Pu; Xu, Bing; Zhang, Zhan-Ming; Zhang, Junliang; Chemical science 15 (2024) 5573–5580; doi:10.1039/d4sc00262h

data_1571212
_publ_section_title
;
 Palladium/XuPhos-catalyzed enantioselective cascade Heck/intermolecular
 C(sp<sup>2</sup>)-H alkylation reaction.
;
_journal_issue                   15
_journal_name_full               'Chemical science'
_journal_page_first              5573
_journal_page_last               5580
_journal_paper_doi               10.1039/d4sc00262h
_journal_volume                  15
_journal_year                    2024
_chemical_absolute_configuration unk
_chemical_formula_moiety         'C24 H17 F4 N O'
_chemical_formula_sum            'C24 H17 F4 N O'
_chemical_formula_weight         411.38
_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             2022-11-29
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2024-01-12 deposited with the CCDC.	2024-03-08 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   6.42860(10)
_cell_length_b                   8.7411(2)
_cell_length_c                   33.5094(6)
_cell_measurement_reflns_used    12072
_cell_measurement_temperature    296.3(6)
_cell_measurement_theta_max      73.0420
_cell_measurement_theta_min      5.2450
_cell_volume                     1882.99(6)
_computing_cell_refinement       'CrysAlisPro 1.171.39.32a (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.32a (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.32a (Rigaku OD, 2017)'
_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      air
_diffrn_ambient_temperature      296.3(6)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_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     13.00  43.00   1.00    1.00    --    0.00  57.00 -30.00   30
  2  \w    -19.00   9.00   1.00    1.00    --    0.00  57.00 -30.00   28
  3  \w    -28.00  89.00   1.00    1.00    --    0.00  77.00   0.00  117
  4  \w    -18.00  82.00   1.00    1.00    --    0.00  37.00 -90.00  100
  5  \w    -19.00  33.00   1.00    1.00    --    0.00  37.00 150.00   52
  6  \w     37.00  88.00   1.00    1.00    --    0.00  37.00  90.00   51
  7  \w    -19.00  21.00   1.00    1.00    --    0.00  37.00  90.00   40
  8  \w     46.00  86.00   1.00    1.00    --    0.00  57.00 -30.00   40
  9  \w    -23.00  34.00   1.00    1.00    --    0.00  57.00-150.00   57
 10  \w     64.00  89.00   1.00    1.00    --    0.00  37.00 150.00   25
 11  \w     68.00  94.00   1.00    3.00    --   95.80  68.00 -78.73   26
 12  \w     74.00 124.00   1.00    3.00    --   95.80  52.00  -6.75   50
 13  \w    140.00 166.00   1.00    3.00    --   95.80  52.00  -6.75   26
 14  \w     63.00  88.00   1.00    3.00    --   95.80  81.00  -6.03   25
 15  \w    124.00 149.00   1.00    3.00    --   95.80  75.00 172.26   25
 16  \w     70.00 181.00   1.00    3.00    --   95.80  62.00 -77.72  111
 17  \w     69.00  94.00   1.00    3.00    --   95.80  67.00-125.40   25
 18  \w     66.00  91.00   1.00    3.00    --   95.80  75.00 172.26   25
 19  \w     63.00  88.00   1.00    3.00    --   95.80  82.00-180.00   25
 20  \w     80.00 128.00   1.00    3.00    --   95.80 -82.00 -90.00   48
 21  \w    126.00 152.00   1.00    3.00    --   95.80  82.00-180.00   26
 22  \w     95.00 126.00   1.00    3.00    --   95.80 -82.00  90.00   31
 23  \w     65.00  90.00   1.00    3.00    --   95.80  77.00 120.00   25
 24  \w    146.00 172.00   1.00    3.00    --   95.80  77.00 120.00   26
 25  \w     71.00 184.00   1.00    3.00    --   95.80  61.00   0.00  113
 26  \w     63.00  88.00   1.00    3.00    --   95.80  82.00  60.00   25
 27  \w      6.00 128.00   1.00    3.00    --   95.80 -82.00-180.00  122
 28  \w     65.00  92.00   1.00    3.00    --   95.80  77.00  30.00   27
 29  \w     95.00 121.00   1.00    3.00    --   95.80  77.00  30.00   26
 30  \w     75.00 102.00   1.00    3.00    --   95.80  45.00 120.00   27
 31  \w     67.00 143.00   1.00    3.00    --   95.80  73.00-118.78   76
 32  \w     71.00 105.00   1.00    3.00    --   95.80  59.00 -47.32   34
 33  \w      7.00  74.00   1.00    3.00    --   95.80 -82.00 -90.00   67
 34  \w     75.00 102.00   1.00    3.00    --   95.80  45.00  90.00   27
 35  \w     65.00  91.00   1.00    3.00    --   95.80  77.00-150.00   26
 36  \w     75.00 185.00   1.00    3.00    --   95.80  45.00  60.00  110
 37  \w     63.00  88.00   1.00    3.00    --   95.80  82.00 -90.00   25
 38  \w    125.00 150.00   1.00    3.00    --   95.80  82.00 -90.00   25
 39  \w     65.00  90.00   1.00    3.00    --   95.80  77.00 -30.00   25
 40  \w    151.00 176.00   1.00    3.00    --   95.80  77.00 -30.00   25
 41  \w     63.00  89.00   1.00    3.00    --   95.80  82.00-120.00   26
 42  \w     63.00  96.00   1.00    3.00    --   95.80  82.00  90.00   33
 43  \w     63.00  88.00   1.00    3.00    --   95.80  82.00 133.04   25
 44  \w     65.00  91.00   1.00    3.00    --   95.80  77.00 150.00   26
 45  \w    111.00 136.00   1.00    3.00    --   95.80  82.00   0.00   25
 46  \w     50.00  86.00   1.00    3.00    --   95.80 -82.00-120.00   36
 47  \w     95.00 128.00   1.00    3.00    --   95.80 -82.00-120.00   33
 48  \w     63.00  89.00   1.00    3.00    --   95.80  82.00 120.00   26
 49  \w      6.00 128.00   1.00    3.00    --   95.80 -82.00  30.00  122
 50  \w     63.00  89.00   1.00    3.00    --   95.80  82.00   0.00   26
 51  \w     71.00 131.00   1.00    3.00    --   95.80  61.00-180.00   60
 52  \w     72.00 105.00   1.00    3.00    --   95.80  61.00-150.00   33
 53  \w     65.00  91.00   1.00    3.00    --   95.80  77.00 -60.00   26
 54  \w    108.00 133.00   1.00    3.00    --   95.80  77.00 -60.00   25
 55  \w     20.00 111.00   1.00    3.00    --   95.80 -61.00  30.00   91
 56  \w     65.00  91.00   1.00    3.00    --   95.80  82.00 -30.00   26
 57  \w     74.00 100.00   1.00    3.00    --   95.80  53.00-152.71   26
 58  \w     72.00  98.00   1.00    3.00    --   95.80  61.00 -30.00   26
 59  \w     65.00  91.00   1.00    3.00    --   95.80  77.00-120.00   26
 60  \w     76.00 163.00   1.00    3.00    --   95.80  45.00 150.00   87
 61  \w    119.00 166.00   1.00    3.00    --   95.80  45.00 120.00   47
 62  \w    110.00 153.00   1.00    3.00    --   95.80  81.00  -6.03   43
 63  \w     75.00 170.00   1.00    3.00    --   95.80  50.00-120.74   95
 64  \w    142.00 178.00   1.00    3.00    --   95.80  67.00-125.40   36
 65  \w    153.00 180.00   1.00    3.00    --   95.80  51.00  95.67   27
 66  \w     74.00  99.00   1.00    3.00    --   95.80  51.00  95.67   25
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RINC): Kappa dual home/near'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1493729000
_diffrn_orient_matrix_UB_12      -0.0148176000
_diffrn_orient_matrix_UB_13      0.0357346000
_diffrn_orient_matrix_UB_21      -0.1316204000
_diffrn_orient_matrix_UB_22      0.1162358000
_diffrn_orient_matrix_UB_23      0.0235533000
_diffrn_orient_matrix_UB_31      -0.1334024000
_diffrn_orient_matrix_UB_32      -0.1316413000
_diffrn_orient_matrix_UB_33      0.0167897000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0608
_diffrn_reflns_av_unetI/netI     0.0250
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       40
_diffrn_reflns_limit_l_min       -40
_diffrn_reflns_number            40249
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        67.067
_diffrn_reflns_theta_max         67.067
_diffrn_reflns_theta_min         5.230
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.985
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.51304
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.32a (Rigaku Oxford Diffraction, 2017)
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    1.451
_exptl_crystal_description       block
_exptl_crystal_F_000             848
_exptl_crystal_size_max          0.26
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.18
_refine_diff_density_max         0.104
_refine_diff_density_min         -0.108
_refine_diff_density_rms         0.026
_refine_ls_abs_structure_details
;
 Flack x determined using 1196 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.07(7)
_refine_ls_extinction_coef       0.0027(4)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2017/1 (Sheldrick 2017)'
_refine_ls_goodness_of_fit_ref   1.060
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     273
_refine_ls_number_reflns         3362
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.060
_refine_ls_R_factor_all          0.0334
_refine_ls_R_factor_gt           0.0302
_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^+0.1736P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0769
_refine_ls_wR_factor_ref         0.0790
_reflns_Friedel_coverage         0.697
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.999
_reflns_number_gt                3080
_reflns_number_total             3362
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc00262h2.cif
_cod_data_source_block           exp_2939
_cod_depositor_comments          'Adding full bibliography for 1571212.cif.'
_cod_database_code               1571212
_shelx_shelxl_version_number     2017/1
_reflns_odcompleteness_completeness 99.90
_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 Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C9(H9A,H9B)
2.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C17(H17), C18(H18), C20(H20), C21(H21),
 C22(H22), C23(H23)
2.c Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C)
;
_shelx_res_checksum              6894
_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 2.818
_oxdiff_exptl_absorpt_empirical_full_min 0.478