Development and Mechanistic Investigations of a Base-Free Suzuki‒Miyaura Cross-Coupling of α,α-Difluoroacetamides via C‒N Bond Cleavage
Reina, Antonio; Krachko, Tetiana; Onida, Killian; Bouyssi, Didier; Jeanneau, Erwann; Monteiro, Nuno; Amgoune, Abderrahmane; ACS Catalysis  (2020) 2189–2197; doi:10.1021/acscatal.9b05159

data_4517334
_publ_section_title
;
 Development and Mechanistic Investigations of a Base-Free Suzuki--Miyaura
 Cross-Coupling of \a,\a-Difluoroacetamides via C--N Bond Cleavage
;
_journal_name_full               'ACS Catalysis'
_journal_page_first              2189
_journal_page_last               2197
_journal_paper_doi               10.1021/acscatal.9b05159
_journal_year                    2020
_chemical_formula_moiety         'C44 H71 Cl F2 O P2 Pd'
_chemical_formula_sum            'C44 H71 Cl F2 O P2 Pd'
_chemical_formula_weight         857.79
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-09-13
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                93.900(3)
_cell_angle_beta                 97.182(4)
_cell_angle_gamma                92.677(4)
_cell_formula_units_Z            4
_cell_length_a                   12.0444(6)
_cell_length_b                   14.0441(6)
_cell_length_c                   25.7109(8)
_cell_measurement_reflns_used    30422
_cell_measurement_temperature    150.01(10)
_cell_measurement_theta_max      29.1900
_cell_measurement_theta_min      2.8870
_cell_volume                     4298.3(3)
_computing_cell_refinement       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_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      150.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4685
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.871
_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    -43.00  66.00   1.00   50.00    --  -10.32  77.00-120.00  109
  2  \w    -13.00  86.00   1.00   50.00    --   11.26  37.00 120.00   99
  3  \w     -4.00  52.00   1.00   50.00    --   11.26 -99.00-180.00   56
  4  \w     -4.00  52.00   1.00   50.00    --   11.26 -99.00   0.00   56
  5  \w    -13.00  86.00   1.00   50.00    --   11.26  37.00-120.00   99
  6  \w    -42.00   7.00   1.00   50.00    --   11.26 120.00 102.00   49
  7  \w    -63.00  36.00   1.00   50.00    --   11.26 -37.00 -60.00   99
  8  \w    -38.00  41.00   1.00   50.00    --  -10.32  57.00  90.00   79
  9  \w     -4.00  52.00   1.00   50.00    --   11.26 -99.00  60.00   56
 10  \w    -13.00  86.00   1.00   50.00    --   11.26  37.00   0.00   99
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Atlas, Gemini ultra'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0432010000
_diffrn_orient_matrix_UB_12      -0.0316177000
_diffrn_orient_matrix_UB_13      -0.0136850000
_diffrn_orient_matrix_UB_21      0.0206136000
_diffrn_orient_matrix_UB_22      0.0082094000
_diffrn_orient_matrix_UB_23      -0.0240622000
_diffrn_orient_matrix_UB_31      0.0352545000
_diffrn_orient_matrix_UB_32      -0.0387756000
_diffrn_orient_matrix_UB_33      0.0033477000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0957
_diffrn_reflns_av_unetI/netI     0.0906
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.871
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       35
_diffrn_reflns_limit_l_min       -35
_diffrn_reflns_number            90811
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.871
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.807
_diffrn_reflns_theta_min         2.715
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.609
_exptl_absorpt_correction_T_max  0.841
_exptl_absorpt_correction_T_min  0.770
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.53 (Rigaku Oxford Diffraction, 2019)
Analytical numeric absorption correction using a multifaceted crystal
			model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
;
_exptl_crystal_colour            'light yellow'
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.326
_exptl_crystal_description       block
_exptl_crystal_F_000             1816
_exptl_crystal_size_max          0.606
_exptl_crystal_size_mid          0.472
_exptl_crystal_size_min          0.367
_refine_diff_density_max         1.638
_refine_diff_density_min         -2.062
_refine_diff_density_rms         0.160
_refine_ls_extinction_coef       0.0030(4)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.158
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     920
_refine_ls_number_reflns         21456
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.158
_refine_ls_R_factor_all          0.1141
_refine_ls_R_factor_gt           0.0716
_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^)+(0.0991P)^2^+3.6600P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1742
_refine_ls_wR_factor_ref         0.2236
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14047
_reflns_number_total             21456
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs9b05159_si_002.cif
_cod_data_source_block           tk232
_cod_depositor_comments
'Adding full bibliography for 4517334--4517335.cif.'
_cod_database_code               4517334
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'Pd1 Cl1 F2 O1 P2 C44 H71'
_reflns_odcompleteness_completeness 99.88
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2.a Ternary CH refined with riding coordinates:
 C9(H9), C15(H15), C21(H21), C27(H27), C33(H33), C39(H39), C53(H53), C59(H59),
 C65(H65), C71(H71), C77(H77), C83(H83)
2.b Secondary CH2 refined with riding coordinates:
 C10(H10A,H10B), C11(H11A,H11B), C12(H12A,H12B), C13(H13A,H13B), C14(H14A,
 H14B), C16(H16A,H16B), C17(H17A,H17B), C18(H18A,H18B), C19(H19A,H19B),
 C20(H20A,H20B), C22(H22A,H22B), C23(H23A,H23B), C24(H24A,H24B), C25(H25A,H25B),
  C26(H26A,H26B), C28(H28A,H28B), C29(H29A,H29B), C30(H30A,H30B), C31(H31A,
 H31B), C32(H32A,H32B), C34(H34A,H34B), C35(H35A,H35B), C36(H36A,H36B),
 C37(H37A,H37B), C38(H38A,H38B), C40(H40A,H40B), C41(H41A,H41B), C42(H42A,H42B),
  C43(H43A,H43B), C44(H44A,H44B), C54(H54A,H54B), C55(H55A,H55B), C56(H56A,
 H56B), C57(H57A,H57B), C58(H58A,H58B), C60(H60A,H60B), C61(H61A,H61B),
 C62(H62A,H62B), C63(H63A,H63B), C64(H64A,H64B), C66(H66A,H66B), C67(H67A,H67B),
  C68(H68A,H68B), C69(H69A,H69B), C70(H70A,H70B), C72(H72A,H72B), C73(H73A,
 H73B), C74(H74A,H74B), C75(H75A,H75B), C76(H76A,H76B), C78(H78A,H78B),
 C79(H79A,H79B), C80(H80A,H80B), C81(H81A,H81B), C82(H82A,H82B), C84(H84A,H84B),
  C85(H85A,H85B), C86(H86A,H86B), C87(H87A,H87B), C88(H88A,H88B)
2.c Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C6(H6), C7(H7), C8(H8), C48(H48), C49(H49), C50(H50),
 C51(H51), C52(H52)
;
_shelx_res_checksum              16054
_shelx_hkl_checksum              24793
_olex2_date_sample_data_collection 2019-09-11
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a nylon loop in perfluoroether oil'
_olex2_submission_original_sample_id TK232
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
;
_oxdiff_exptl_absorpt_empirical_full_max 1.128
_oxdiff_exptl_absorpt_empirical_full_min 0.723