A Bulky Chiral N-Heterocyclic Carbene Palladium Catalyst Enables Highly Enantioselective Suzuki-Miyaura Cross-Coupling Reactions for the Synthesis of Biaryl Atropisomers.
Shen, Di; Xu, Youjun; Shi, Shi-Liang; Journal of the American Chemical Society 141 (2019) 14938–14945; doi:10.1021/jacs.9b08578

data_4127632
_publ_section_title
;
 A Bulky Chiral N-Heterocyclic Carbene Palladium Catalyst Enables Highly
 Enantioselective Suzuki-Miyaura Cross-Coupling Reactions for the
 Synthesis of Biaryl Atropisomers.
;
_journal_issue                   37
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              14938
_journal_page_last               14945
_journal_paper_doi               10.1021/jacs.9b08578
_journal_volume                  141
_journal_year                    2019
_chemical_absolute_configuration rmad
_chemical_formula_moiety         'C90 H124 Cl N2 Pd'
_chemical_formula_sum            'C90 H124 Cl N2 Pd'
_chemical_formula_weight         1375.75
_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'
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-02-25
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   17.561(2)
_cell_length_b                   18.084(2)
_cell_length_c                   29.865(3)
_cell_measurement_reflns_used    9607
_cell_measurement_temperature    170(2)
_cell_measurement_theta_max      52.13
_cell_measurement_theta_min      3.05
_cell_volume                     9484.3(18)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_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_temperature      170.01
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.986
_diffrn_measurement_device_type  'Bruker D8 Venture'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           GaK\a
_diffrn_radiation_wavelength     1.34139
_diffrn_reflns_av_R_equivalents  0.1263
_diffrn_reflns_av_unetI/netI     0.1083
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.986
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -36
_diffrn_reflns_number            81098
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.981
_diffrn_reflns_theta_full        53.594
_diffrn_reflns_theta_max         55.224
_diffrn_reflns_theta_min         3.052
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.397
_exptl_absorpt_correction_T_max  0.7508
_exptl_absorpt_correction_T_min  0.4413
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
 TWINABS-2012/1 (Bruker,2012) was used for absorption correction.

Final HKLF 4 output contains 182596 reflections, Rint = 0.1826
 (65158 with I > 3sig(I), Rint = 0.1368)
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    0.963
_exptl_crystal_description       block
_exptl_crystal_F_000             2964
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.05
_refine_diff_density_max         3.177
_refine_diff_density_min         -1.462
_refine_diff_density_rms         0.121
_refine_ls_abs_structure_details
;
 Flack x determined using 3222 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.286(7)
_refine_ls_extinction_coef       0.0015(3)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2016/6 (Sheldrick 2016)'
_refine_ls_goodness_of_fit_ref   1.102
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     866
_refine_ls_number_reflns         17907
_refine_ls_number_restraints     356
_refine_ls_restrained_S_all      1.117
_refine_ls_R_factor_all          0.1665
_refine_ls_R_factor_gt           0.1200
_refine_ls_shift/su_max          0.081
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1834P)^2^+12.8240P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3163
_refine_ls_wR_factor_ref         0.3483
_reflns_Friedel_coverage         0.830
_reflns_Friedel_fraction_full    0.998
_reflns_Friedel_fraction_max     0.975
_reflns_number_gt                10825
_reflns_number_total             17907
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b08578_si_002.cif
_cod_data_source_block           mj19098_0m
_cod_original_cell_volume        9484.7(19)
_cod_database_code               4127632
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.933
_shelx_estimated_absorpt_t_min   0.873
_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. Restrained distances
 C89-C87 = C88-C87 = C90-C87
 1.53 with sigma of 0.02
 C88-C90
 2.44 with sigma of 0.02
 C23-C31 = C34-C31 = C32-C31 = C31-C33
 1.53 with sigma of 0.02
 H22-H33B
 2 with sigma of 0.02
 C89-C88 \\sim C88-C90
 with sigma of 0.02
 C90-C89 \\sim C89-C88
 with sigma of 0.02
3. Rigid bond restraints
 C47, C50
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
 C47, C49
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
4. Uiso/Uaniso restraints and constraints
C87 \\sim C88 \\sim C89 \\sim C90: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02
C79 \\sim C87 \\sim C88 \\sim C89 \\sim C90: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02
C77 \\sim C78 \\sim C79 \\sim C80 \\sim C81 \\sim C82: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02
C21 \\sim C22 \\sim C23 \\sim C24 \\sim C25 \\sim C26 \\sim C31 \\sim C32 \\sim
C33 \\sim C34: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C13 \\sim C14 \\sim C15 \\sim C16 \\sim C17 \\sim C18: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02
C37 \\sim C38 \\sim C39 \\sim C40 \\sim C41 \\sim C42: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02
C58 \\sim C59 \\sim C60 \\sim C61 \\sim C62 \\sim C63 \\sim C64: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02
C2 \\sim C3 \\sim C4: within 2A with sigma of 0.01 and sigma for terminal atoms
of 0.02
C3 \\sim C4: within 2A with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C45) \\sim Ueq, Uanis(C43) \\sim Ueq, Uanis(C44) \\sim Ueq, Uanis(C46)
\\sim Ueq, Uanis(C49) \\sim Ueq, Uanis(C48) \\sim Ueq, Uanis(C71) \\sim Ueq,
Uanis(C70) \\sim Ueq, Uanis(C27) \\sim Ueq, Uanis(C90) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
Uanis(C30) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C3) \\sim Ueq, Uanis(C4) \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.01
Uanis(C58) \\sim Ueq, Uanis(C11) \\sim Ueq, Uanis(C1) \\sim Ueq: with sigma of
0.005 and sigma for terminal atoms of 0.01
5.a Ternary CH refined with riding coordinates:
 C3(H3), C4(H4), C19(H19), C35(H35), C58(H58), C75(H75)
5.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C9(H9A,H9B), C11(H11A,H11B), C12(H12A,H12B)
5.c Aromatic/amide H refined with riding coordinates:
 C6(H6), C7(H7), C8(H8), C10(H10), C15(H15), C17(H17), C22(H22), C24(H24),
 C26(H26), C38(H38), C40(H40), C42(H42), C54(H54), C56(H56), C60(H60), C62(H62),
  C64(H64), C78(H78), C80(H80), C82(H82)
5.d Fitted hexagon refined as free rotating group:
 C5(C6,C7,C8,C9,C10)
5.e Idealised Me refined as rotating group:
 C20(H20A,H20B,H20C), C28(H28A,H28B,H28C), C29(H29A,H29B,H29C), C30(H30A,H30B,
 H30C), C32(H32A,H32B,H32C), C33(H33A,H33B,H33C), C34(H34A,H34B,H34C), C36(H36A,
 H36B,H36C), C44(H44A,H44B,H44C), C45(H45A,H45B,H45C), C46(H46A,H46B,H46C),
 C48(H48A,H48B,H48C), C49(H49A,H49B,H49C), C50(H50A,H50B,H50C), C51(H51A,H51B,
 H51C), C66(H66A,H66B,H66C), C67(H67A,H67B,H67C), C68(H68A,H68B,H68C), C70(H70A,
 H70B,H70C), C71(H71A,H71B,H71C), C72(H72A,H72B,H72C), C73(H73A,H73B,H73C),
 C74(H74A,H74B,H74C), C76(H76A,H76B,H76C), C84(H84A,H84B,H84C), C85(H85A,H85B,
 H85C), C86(H86A,H86B,H86C), C88(H88A,H88B,H88C), C89(H89A,H89B,H89C), C90(H90A,
 H90B,H90C)
;
_shelx_res_checksum              35869
_shelx_hkl_checksum              81201
_shelx_fab_checksum              91734
_olex2_submission_special_instructions 'No special instructions were received'