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_4517335
_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
'0.5(C52 H76 F4 O3 P2 Pd), 0.5(C52 H74 F4 O3 P2 Pd), 0.5(C2 H3 N)'
_chemical_formula_sum            'C53 H76.5 F4 N0.5 O3 P2 Pd'
_chemical_formula_weight         1012.98
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2019-09-25
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                81.169(5)
_cell_angle_beta                 89.195(6)
_cell_angle_gamma                73.803(7)
_cell_formula_units_Z            4
_cell_length_a                   13.4397(10)
_cell_length_b                   18.3716(12)
_cell_length_c                   21.7868(13)
_cell_measurement_reflns_used    12355
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      26.7340
_cell_measurement_theta_min      3.2350
_cell_volume                     5102.3(6)
_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      150.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4685
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.848
_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    -38.00  63.00   1.00   62.50    --  -10.32  57.00  60.00  101
  2  \w    -99.00 -35.00   1.00   62.50    --  -10.32-178.00  30.00   64
  3  \w    -38.00  63.00   1.00   62.50    --  -10.32  57.00 150.00  101
  4  \w    -82.00  18.00   1.00   62.50    --  -10.32 -57.00 -90.00  100
  5  \w    -99.00 -35.00   1.00   62.50    --  -10.32-178.00-180.00   64
  6  \w    -99.00 -35.00   1.00   62.50    --  -10.32-178.00 -60.00   64
  7  \w     53.00  92.00   1.00   62.50    --   11.34-178.00  90.00   39
  8  \w     49.00  74.00   1.00   62.50    --   11.34  57.00 150.00   25
  9  \w    -17.00  50.00   1.00   62.50    --   11.34  57.00-120.00   67
 10  \w     -7.00  25.00   1.00   62.50    --   11.34  37.00   0.00   32
;
_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      -0.0384887000
_diffrn_orient_matrix_UB_12      0.0012035000
_diffrn_orient_matrix_UB_13      -0.0223756000
_diffrn_orient_matrix_UB_21      0.0307238000
_diffrn_orient_matrix_UB_22      0.0120318000
_diffrn_orient_matrix_UB_23      -0.0240461000
_diffrn_orient_matrix_UB_31      0.0244505000
_diffrn_orient_matrix_UB_32      -0.0388637000
_diffrn_orient_matrix_UB_33      -0.0027593000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0935
_diffrn_reflns_av_unetI/netI     0.1285
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.848
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            84745
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.848
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.817
_diffrn_reflns_theta_min         3.045
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.482
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.712
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.53 (Rigaku Oxford Diffraction, 2019)
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    1.319
_exptl_crystal_description       needle
_exptl_crystal_F_000             2136
_exptl_crystal_size_max          0.592
_exptl_crystal_size_mid          0.166
_exptl_crystal_size_min          0.062
_refine_diff_density_max         1.604
_refine_diff_density_min         -1.985
_refine_diff_density_rms         0.127
_refine_ls_extinction_coef       0.0027(3)
_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   1.061
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1204
_refine_ls_number_reflns         24839
_refine_ls_number_restraints     148
_refine_ls_restrained_S_all      1.065
_refine_ls_R_factor_all          0.1513
_refine_ls_R_factor_gt           0.0762
_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^)+(0.0982P)^2^+2.8038P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1712
_refine_ls_wR_factor_ref         0.2339
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13419
_reflns_number_total             24839
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs9b05159_si_003.cif
_cod_data_source_block           tk235
_cod_depositor_comments
'Adding full bibliography for 4517334--4517335.cif.'
_cod_original_formula_sum        'C53 H76.50 F4 N0.50 O3 P2 Pd'
_cod_database_code               4517335
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'Pd1 P2 O3 N0.5 F4 H77 C53'
_reflns_odcompleteness_completeness 99.49
_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
 At 1.5 times of:
  All C(H,H,H) groups, All C(H,H,H,H) groups
2. Restrained distances
 F8B-C98 \\sim F8A-C98 \\sim F7A-C98 \\sim F7B-C98
 with sigma of 0.02
 C97A-C98 \\sim C97B-C98
 with sigma of 0.02
 O5A-C97B \\sim O5B-C97A
 with sigma of 0.02
 O6A-C97B \\sim O6B-C97A
 with sigma of 0.02
 Pd2-O5A \\sim Pd2-O5B
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
F7A \\sim F7B \\sim F8A \\sim O5A \\sim O5B \\sim O6A \\sim O6B \\sim C97A
\\sim C97B \\sim C98: within 1.7A with sigma of 0.01 and sigma for terminal
atoms of 0.02
C53 \\sim C54 \\sim C55 \\sim C56 \\sim C57 \\sim C58: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02
4. Others
 Sof(F7B)=Sof(F8B)=Sof(O5B)=Sof(O6B)=Sof(C97A)=1-FVAR(1)
 Sof(F7A)=Sof(F8A)=Sof(O5A)=Sof(O6A)=Sof(C97B)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C1(H1), C7(H7), C13(H13), C19(H19), C25(H25), C31(H31), C53(H53), C59(H59),
 C65(H65), C71(H71), C77(H77), C83(H83)
5.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C3(H3A,H3B), C4(H4A,H4B), C5(H5A,H5B), C6(H6A,H6B), C8(H8A,H8B),
 C10(H10A,H10B), C12(H12A,H12B), C14(H14A,H14B), C15(H15A,H15B), C16(H16A,H16B),
  C17(H17A,H17B), C18(H18A,H18B), C20(H20A,H20B), C21(H21A,H21B), C22(H22A,
 H22B), C23(H23A,H23B), C24(H24A,H24B), C26(H26A,H26B), C27(H27A,H27B),
 C28(H28A,H28B), C29(H29A,H29B), C30(H30A,H30B), C32(H32A,H32B), C33(H33A,H33B),
  C34(H34A,H34B), C35(H35A,H35B), C36(H36A,H36B), C54(H54A,H54B), 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)
5.c Aromatic/amide H refined with riding coordinates:
 C40(H40), C41(H41), C42(H42), C43(H43), C44(H44), C48(H48), C49(H49),
 C50(H50), C51(H51), C52(H52), C55(H55), C56(H56), C92(H92), C93(H93), C94(H94),
  C95(H95), C96(H96), C100(H100), C101(H101), C102(H102), C103(H103), C104(H104)
5.d Idealised Me refined as rotating group:
 C106(H10C,H10D,H10E)
;
_shelx_res_checksum              76978
_shelx_hkl_checksum              69100
_olex2_date_sample_data_collection 2019-09-23
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a nylon loop in perfluoroether oil'
_olex2_submission_original_sample_id TK235
_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 1.314
_oxdiff_exptl_absorpt_empirical_full_min 0.772