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_1576121
_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_formula_moiety         'C46 H70 Br2 N2 O2 P2 Pd2, C4 H10 O'
_chemical_formula_sum            'C50 H80 Br2 N2 O3 P2 Pd2'
_chemical_formula_weight         1191.72
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-05-29
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-07-24 deposited with the CCDC.	2025-10-24 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 99.0030(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   19.26540(10)
_cell_length_b                   15.40890(10)
_cell_length_c                   18.56470(10)
_cell_measurement_reflns_used    50262
_cell_measurement_temperature    120.00(11)
_cell_measurement_theta_max      74.6310
_cell_measurement_theta_min      2.3350
_cell_volume                     5443.20(6)
_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_temperature      120.15
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 150'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.987
_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    -90.00 -39.00   0.50    7.00    --  -52.73   0.00 -60.00  102
  2  \w    -74.00 -24.00   0.50    7.00    --  -52.73   0.00-150.00  100
  3  \w    -72.00 -46.00   0.50    7.00    --  -52.73 125.00 -60.00   52
  4  \w    -45.00 -19.00   0.50    7.00    --  -52.73 118.00 -50.00   52
  5  \w    -69.00 -36.00   0.50    7.00    --  -52.73 125.00   0.00   66
  6  \w     34.00 109.00   0.50    7.00    --   64.59  15.00-180.00  150
  7  \w     35.00  91.00   0.50    7.00    --   64.59-125.00 -30.00  112
  8  \w     36.00  62.00   0.50    7.00    --   64.59-125.00-120.00   52
  9  \w     35.00  60.00   0.50    7.00    --   64.59-125.00 150.00   50
 10  \w     36.00  91.00   0.50    7.00    --   64.59-125.00 -90.00  110
 11  \w     43.00  68.00   0.50    7.00    --   64.59 -94.00 150.00   50
 12  \w     64.00  97.00   0.50    7.00    --   72.67-125.00 -30.00   66
 13  \w     69.00  94.00   0.50    7.00    --   77.48-158.00  69.00   50
 14  \w     42.00  77.00   0.50    7.00    --   77.48 -94.00  90.00   70
 15  \w     59.00 104.00   0.50    7.00    --   77.48-125.00 -30.00   90
 16  \w     42.00  86.00   0.50    7.00    --   77.48-125.00  60.00   88
 17  \w     49.00  75.00   0.50    7.00    --   77.48 -94.00 -30.00   52
 18  \w     79.00 104.00   0.50    7.00    --   77.48-125.00  30.00   50
 19  \w     37.00  62.00   0.50    7.00    --   77.48-125.00 -60.00   50
 20  \w     61.00 104.00   0.50    7.00    --   77.48-125.00 -90.00   86
 21  \w     58.00 103.00   0.50    7.00    --   77.48-125.00   0.00   90
 22  \w     79.00 104.00   0.50    7.00    --   77.48-125.00 -60.00   50
 23  \w     40.00  98.00   0.50    7.00    --   77.48-125.00-150.00  116
 24  \w     51.00  76.00   0.50    7.00    --   77.48  15.00  30.00   50
 25  \w     56.00  81.00   0.50    7.00    --   77.48 -94.00   0.00   50
 26  \w     49.00  74.00   0.50    7.00    --   77.48 -94.00  60.00   50
 27  \w     72.00 100.00   0.50    7.00    --   77.48-118.00-136.00   56
 28  \w     53.00  82.00   0.50    7.00    --   77.48 -94.00 150.00   58
 29  \w     55.00  80.00   0.50    7.00    --   77.48 -94.00-180.00   50
 30  \w     40.00  68.00   0.50    7.00    --   77.48-118.00-136.00   56
 31  \w     51.00  76.00   0.50    7.00    --   77.48 -94.00-120.00   50
 32  \w     94.00 119.00   0.50    7.00    --   77.48  15.00   0.00   50
 33  \w     43.00  85.00   0.50    7.00    --   77.48 -94.00 -90.00   84
 34  \w     74.00  99.00   0.50    7.00    --   77.48-125.00  90.00   50
 35  \w     63.00  95.00   0.50    7.00    --   77.50  12.00 175.78   64
 36  \w     65.00 124.00   0.50    7.00    --   77.50  22.00-163.18  118
 37  \w     42.00 101.00   0.50    7.00    --   77.50   4.00 112.84  118
 38  \w     61.00 110.00   0.50    7.00    --   77.50  20.00  39.34   98
 39  \w     41.00  84.00   0.50    7.00    --   77.50   1.00  40.35   86
 40  \w     61.00 122.00   0.50    7.00    --   77.50  19.00 -63.71  122
 41  \w     84.00 110.00   0.50    7.00    --   77.50  21.00 -35.69   52
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix-Arc 150'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0676
_diffrn_reflns_av_unetI/netI     0.0308
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            65425
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.782
_diffrn_reflns_theta_min         2.322
_exptl_absorpt_coefficient_mu    7.905
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.221
_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            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.454
_exptl_crystal_description       plate
_exptl_crystal_F_000             2440
_exptl_crystal_size_max          0.448
_exptl_crystal_size_mid          0.096
_exptl_crystal_size_min          0.031
_refine_diff_density_max         0.942
_refine_diff_density_min         -1.423
_refine_diff_density_rms         0.112
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.079
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     570
_refine_ls_number_reflns         11035
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.079
_refine_ls_R_factor_all          0.0363
_refine_ls_R_factor_gt           0.0353
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0657P)^2^+4.3286P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1022
_refine_ls_wR_factor_ref         0.1031
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10617
_reflns_number_total             11035
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc07577g2.cif
_cod_data_source_block           complex17
_cod_depositor_comments
'Adding full bibliography for 1576120--1576121.cif.'
_cod_original_cell_volume        5443.19(6)
_cod_database_code               1576121
_shelx_shelxl_version_number     2019/2
_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:
 C01L(H01D,H01E), C01N(H01F,H01G)
2.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C5(H5), C6(H6), C18(H18), C19(H19), C21(H21), C22(H22),
 C27(H27), C28(H28), C30(H30), C31(H31), C43(H43), C44(H44), C48(H48), C49(H49)
2.c Idealised Me refined as rotating group:
 C01C(H01A,H01B,H01C), C8(H8A,H8B,H8C), C10(H10A,H10B,H10C), C11(H11A,H11B,
 H11C), C12(H12A,H12B,H12C), C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C16(H16A,
 H16B,H16C), C24(H24A,H24B,H24C), C25(H25A,H25B,H25C), C33(H33A,H33B,H33C),
 C35(H35A,H35B,H35C), C36(H36A,H36B,H36C), C37(H37A,H37B,H37C), C39(H39A,H39B,
 H39C), C40(H40A,H40B,H40C), C41(H41A,H41B,H41C), C47(H47A,H47B,H47C),
 C01O(H01H,H01I,H01J), C01P(H01K,H01L,H01M)
;
_shelx_res_checksum              28834
_shelx_hkl_checksum              38329
_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
;