Pd-catalyzed regiodivergent arylation of cyclic allylboronates.
Zhang, Cheng; Leforestier, Baptiste; Besnard, Céline; Mazet, Clément; Chemical science 16 (2025) 22656–22665; doi:10.1039/d5sc07577g

data_1576120
_publ_section_title
;
 Pd-catalyzed regiodivergent arylation of cyclic allylboronates.
;
_journal_issue                   47
_journal_name_full               'Chemical science'
_journal_page_first              22656
_journal_page_last               22665
_journal_paper_doi               10.1039/d5sc07577g
_journal_volume                  16
_journal_year                    2025
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C28 H37 Br N P Pd'
_chemical_formula_sum            'C28 H37 Br N P Pd'
_chemical_formula_weight         604.86
_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             2025-06-25
_audit_creation_method
;
Olex2 1.5
(compiled 2025.05.31 svn.r86d253d1 for OlexSys, GUI svn.r7254)
;
_audit_update_record
;
2025-07-24 deposited with the CCDC.	2025-10-24 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   10.12340(10)
_cell_length_b                   10.90100(10)
_cell_length_c                   51.1310(3)
_cell_measurement_reflns_used    122974
_cell_measurement_temperature    119.99(10)
_cell_measurement_theta_max      74.6540
_cell_measurement_theta_min      2.6020
_cell_volume                     5642.57(8)
_computing_cell_refinement       'CrysAlisPro 1.171.42.100a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.100a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.100a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/2 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      119.99(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 150'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.997
_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      9.00  36.00   0.50    1.14    --    4.00  30.00 170.38   54
  2  \w     11.00  37.00   0.50    1.14    --    4.00  30.00  44.46   52
  3  \w      5.00  31.00   0.50    1.14    --   -4.00  33.00 -98.57   52
  4  \w      9.00  34.00   0.50    1.14    --    4.00  30.00   2.45   50
  5  \w      1.00  27.00   0.50    1.14    --   -8.00  35.00 -53.59   52
  6  \w      1.00  27.00   0.50    1.14    --   -8.00  35.00-152.33   52
  7  \w      1.00  27.00   0.50    1.14    --   -8.00  35.00 111.18   52
  8  \w     11.00  36.00   0.50    1.14    --    8.00  29.00-132.88   50
  9  \w     15.00  40.00   0.50    1.14    --   16.00  27.00  94.00   50
 10  \w     17.00  48.00   0.50    1.14    --   20.00  26.00 -65.26   62
 11  \w     17.00  45.00   0.50    1.14    --   20.00  26.00 134.43   56
 12  \w     -8.00  18.00   0.50    1.14    --  -20.00  42.00  12.79   52
 13  \w    -12.00  15.00   0.50    1.14    --  -24.00  45.00 122.48   54
 14  \w    -50.00 -24.00   0.50    1.14    --  -32.00 -25.00 -20.77   52
 15  \w    -51.00 -24.00   0.50    1.14    --  -32.00 -25.00-112.23   54
 16  \w    -51.00 -26.00   0.50    1.14    --  -32.00 -25.00-162.27   50
 17  \w     24.00  56.00   0.50    1.14    --   36.00  24.00-172.88   64
 18  \w    -30.00   2.00   0.50    1.14    --  -40.00  59.00-114.82   64
 19  \w    -30.00   2.00   0.50    1.14    --  -40.00  58.00 -37.69   64
 20  \w    -29.00   2.00   0.50    1.14    --  -40.00  59.00  25.13   62
 21  \w    -53.00 -28.00   0.50    1.14    --  -40.00 -24.00  83.94   50
 22  \w    -62.00 -34.00   0.50    1.14    --  -48.00 -23.00 173.05   56
 23  \w    -62.00 -37.00   0.50    1.14    --  -48.00 -23.00 135.68   50
 24  \w    -62.00 -37.00   0.50    1.14    --  -48.00 -23.00 -19.86   50
 25  \w     34.00  59.00   0.50    1.14    --   48.00  23.00-147.16   50
 26  \w    -62.00 -36.00   0.50    1.14    --  -48.00 -23.00 147.60   52
 27  \w    -62.00 -34.00   0.50    1.14    --  -48.00 -23.00 -56.70   56
 28  \w    -60.00 -34.00   0.50    1.14    --  -48.00 -23.00-133.75   52
 29  \w    -70.00 -45.00   0.50    1.14    --  -60.00 -22.00  83.13   50
 30  \w    -69.00 -44.00   0.50    1.14    --  -60.00 -22.00 119.70   50
 31  \w    -46.00 -20.00   0.50    1.14    --  -60.50  64.00   8.49   52
 32  \w    -47.00 -19.00   0.50    1.14    --  -60.50  56.00 104.08   56
 33  \w    -39.00 -14.00   0.50    1.14    --  -60.50  36.00-109.23   50
 34  \w    -38.00 -13.00   0.50    1.14    --  -60.50  36.00 -39.57   50
 35  \w    -40.00 -14.00   0.50    1.14    --  -60.50  37.00 -51.04   52
 36  \w    -39.00 -14.00   0.50    1.14    --  -60.50  36.00-154.40   50
 37  \w    -40.00 -15.00   0.50    1.14    --  -60.50  37.00-146.41   50
 38  \w    -40.00 -15.00   0.50    1.14    --  -60.50  37.00 158.24   50
 39  \w    -40.00 -14.00   0.50    1.14    --  -60.50  38.00  89.16   52
 40  \w    -52.00 -27.00   0.50    1.14    --  -60.50  63.00-145.16   50
 41  \w    -47.00 -19.00   0.50    1.14    --  -60.50  60.00 118.33   56
 42  \w    -39.00 -14.00   0.50    1.14    --  -60.50  36.00-179.27   50
 43  \w     31.00  70.00   0.50    1.14    --   64.48 -94.00 150.00   78
 44  \w     41.00  91.00   0.50    1.14    --   64.48-125.00 -90.00  100
 45  \w     49.00  90.00   0.50    1.14    --   64.48-125.00  60.00   82
 46  \w     58.00  91.00   0.50    1.14    --   64.48-125.00   0.00   66
 47  \w     59.00  88.00   0.50    1.14    --   70.96  21.00 -50.61   58
 48  \w     53.00  87.00   0.50    1.14    --   70.96  21.00  51.54   68
 49  \w     55.00 116.00   0.50    1.14    --   70.96  21.00  93.71  122
 50  \w     53.00 116.00   0.50    1.14    --   70.96  21.00 -16.00  126
 51  \w     53.00 103.00   0.50    1.14    --   70.96  21.00 152.58  100
 52  \w     92.00 117.00   0.50    1.14    --   70.96  21.00 -50.61   50
 53  \w     56.00  98.00   0.50    1.14    --   72.65-125.00 -30.00   84
 54  \w     35.00  98.00   0.50    1.14    --   72.65-125.00 120.00  126
 55  \w     44.00  80.00   0.50    1.14    --   72.65 -94.00-180.00   72
 56  \w     39.00  66.00   0.50    1.14    --   77.44-125.00  60.00   54
 57  \w     36.00 102.00   0.50    1.14    --   77.44-125.00 -30.00  132
 58  \w     36.00 104.00   0.50    1.14    --   77.44-125.00-120.00  136
 59  \w     79.00 104.00   0.50    1.14    --   77.44-125.00-180.00   50
 60  \w     36.00  75.00   0.50    1.14    --   77.44-125.00-180.00   78
 61  \w     36.00 104.00   0.50    1.14    --   77.44-125.00  30.00  136
 62  \w     40.00 102.00   0.50    1.14    --   77.44-125.00 -90.00  124
 63  \w     79.00 104.00   0.50    1.14    --   77.44-125.00  90.00   50
 64  \w     36.00  75.00   0.50    1.14    --   77.44-125.00  90.00   78
 65  \w     37.00 104.00   0.50    1.14    --   77.44-125.00 150.00  134
 66  \w     36.00 104.00   0.50    1.14    --   77.44-125.00 -60.00  136
 67  \w     79.00 104.00   0.50    1.14    --   77.44-125.00-150.00   50
 68  \w     36.00  72.00   0.50    1.14    --   77.44-125.00-150.00   72
 69  \w     36.00 104.00   0.50    1.14    --   77.44-125.00 120.00  136
 70  \w     69.00 103.00   0.50    1.14    --   77.44-125.00  60.00   68
 71  \w     37.00  78.00   0.50    1.14    --   77.50-125.00   4.53   82
 72  \w     77.00 106.00   0.50    1.14    --   77.50-126.00  -8.82   58
 73  \w     40.00  70.00   0.50    1.14    --   77.50-126.00  -8.82   60
 74  \w     56.00 119.00   0.50    1.14    --   77.50  20.00  18.48  126
 75  \w     56.00 117.00   0.50    1.14    --   77.50   3.00-143.58  122
 76  \w     43.00 119.00   0.50    1.14    --   77.50   6.00  17.31  152
 77  \w     62.00  88.00   0.50    1.14    --   77.50  22.00  52.04   52
 78  \w     48.00 102.00   0.50    1.14    --   77.50   3.00 162.61  108
 79  \w     92.00 118.00   0.50    1.14    --   77.50  22.00 -65.28   52
 80  \w     62.00  87.00   0.50    1.14    --   77.50  22.00 -65.28   50
 81  \w     62.00 113.00   0.50    1.14    --   77.50  22.00 158.15  102
 82  \w     62.00 124.00   0.50    1.14    --   77.50  22.00-151.73  124
 83  \w     42.00 117.00   0.50    1.14    --   77.50   3.00 -63.07  150
 84  \w     63.00  98.00   0.50    1.14    --   77.50  21.00  76.82   70
 85  \w     62.00 110.00   0.50    1.14    --   77.50  22.00 -43.68   96
 86  \w     62.00 108.00   0.50    1.14    --   77.50  22.00 113.04   92
 87  \w     62.00 107.00   0.50    1.14    --   77.50  22.00-110.51   90
 88  \w     42.00 116.00   0.50    1.14    --   77.50   3.00  96.51  148
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix-Arc 150'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0569040000
_diffrn_orient_matrix_UB_12      -0.1310333000
_diffrn_orient_matrix_UB_13      0.0005832000
_diffrn_orient_matrix_UB_21      0.0397283000
_diffrn_orient_matrix_UB_22      -0.0174730000
_diffrn_orient_matrix_UB_23      -0.0288438000
_diffrn_orient_matrix_UB_31      0.1354807000
_diffrn_orient_matrix_UB_32      -0.0500012000
_diffrn_orient_matrix_UB_33      0.0086539000
_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  0.0720
_diffrn_reflns_av_unetI/netI     0.0205
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       63
_diffrn_reflns_limit_l_min       -63
_diffrn_reflns_number            160153
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.910
_diffrn_reflns_theta_min         3.458
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    7.599
_exptl_absorpt_correction_T_max  0.664
_exptl_absorpt_correction_T_min  0.062
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.100a (Rigaku Oxford Diffraction, 2023)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.424
_exptl_crystal_description       block
_exptl_crystal_F_000             2464
_exptl_crystal_size_max          0.327
_exptl_crystal_size_mid          0.227
_exptl_crystal_size_min          0.196
_refine_diff_density_max         1.422
_refine_diff_density_min         -1.404
_refine_diff_density_rms         0.092
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.

Two complexes with the same configuration are present in the unit cell.
;
_refine_ls_abs_structure_Flack   0.021(10)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.102
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     592
_refine_ls_number_reflns         11544
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.102
_refine_ls_R_factor_all          0.0416
_refine_ls_R_factor_gt           0.0415
_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^)+(0.0559P)^2^+10.5800P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1099
_refine_ls_wR_factor_ref         0.1100
_reflns_Friedel_coverage         0.777
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.989
_reflns_number_gt                11508
_reflns_number_total             11544
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc07577g2.cif
_cod_data_source_block           complex16
_cod_depositor_comments
'Adding full bibliography for 1576120--1576121.cif.'
_cod_database_code               1576120
_shelx_shelxl_version_number     2019/2
_chemical_oxdiff_formula         'Au1 Cl1 C48 H56 N2'
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.979(10)
 0.021(10)
2. 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
3.a Ternary CH refined with riding coordinates:
 C11(H11), C11B(H11B)
3.b Secondary CH2 refined with riding coordinates:
 C10(H10A,H10B), C10B(H10C,H10D)
3.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C6(H6), C17(H17), C18(H18), C21(H21),
 C22(H22), C24(H24), C25(H25), C27(H27), C28(H28), C2B(H2B), C3B(H3B), C4B(H4B),
  C5B(H5B), C6B(H6B), C17B(H17B), C18B(H18B), C21B(H21B), C22B(H22B),
 C24B(H24B), C25B(H25B), C27B(H27B), C28B(H28B)
3.d Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C13(H13A,H13B,H13C), C14(H14A,H14B,H14C),
 C15(H15A,H15B,H15C), C20(H20A,H20B,H20C), C29(H29A,H29B,H29C), C8B(H8BA,H8BB,
 H8BC), C9B(H9BA,H9BB,H9BC), C13B(H13D,H13E,H13F), C14B(H14D,H14E,H14F),
 C15B(H15D,H15E,H15F), C20B(H20D,H20E,H20F), C29B(H29D,H29E,H29F)
;
_shelx_res_checksum              18857
_shelx_hkl_checksum              20939
_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 2.375
_oxdiff_exptl_absorpt_empirical_full_min 0.548