Pd(II)-Catalyzed Enantioselective Alkynylation of Unbiased Methylene C(sp<sup>3</sup>)-H Bonds Using 3,3'-Fluorinated-BINOL as a Chiral Ligand.
Han, Ye-Qiang; Ding, Yi; Zhou, Tao; Yan, Sheng-Yi; Song, Hong; Shi, Bing-Feng; Journal of the American Chemical Society 141 (2019) 4558–4563; doi:10.1021/jacs.9b01124

data_4128933
_publ_section_title
;
 Pd(II)-Catalyzed Enantioselective Alkynylation of Unbiased Methylene
 C(sp<sup>3</sup>)-H Bonds Using 3,3'-Fluorinated-BINOL as a Chiral
 Ligand.
;
_journal_issue                   11
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              4558
_journal_page_last               4563
_journal_paper_doi               10.1021/jacs.9b01124
_journal_volume                  141
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C33 H42 N2 O2 Si'
_chemical_formula_sum            'C33 H42 N2 O2 Si'
_chemical_formula_weight         526.77
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2018-12-20
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 112.699(2)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   25.9190(11)
_cell_length_b                   9.9765(4)
_cell_length_c                   26.3509(11)
_cell_measurement_reflns_used    9201
_cell_measurement_temperature    170(2)
_cell_measurement_theta_max      72.15
_cell_measurement_theta_min      4.43
_cell_volume                     6286.1(5)
_computing_cell_refinement       'SAINT V8.38A (?, 2016)'
_computing_data_reduction        'SAINT V8.38A (?, 2016)'
_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      170.0
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0532
_diffrn_reflns_av_unetI/netI     0.0365
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       31
_diffrn_reflns_limit_h_min       -27
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            147325
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         72.200
_diffrn_reflns_theta_min         1.817
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.880
_exptl_absorpt_correction_T_max  0.7536
_exptl_absorpt_correction_T_min  0.5088
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1380 before and 0.0876 after correction.
The Ratio of minimum to maximum transmission is 0.6752.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'light yellow'
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.113
_exptl_crystal_description       block
_exptl_crystal_F_000             2272
_exptl_crystal_size_max          0.413
_exptl_crystal_size_mid          0.322
_exptl_crystal_size_min          0.222
_refine_diff_density_max         1.874
_refine_diff_density_min         -1.063
_refine_diff_density_rms         0.103
_refine_ls_abs_structure_details
;
 Flack x determined using 9188 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.095(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.381
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1457
_refine_ls_number_reflns         24689
_refine_ls_number_restraints     420
_refine_ls_restrained_S_all      1.381
_refine_ls_R_factor_all          0.1056
_refine_ls_R_factor_gt           0.1016
_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^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2930
_refine_ls_wR_factor_ref         0.3039
_reflns_Friedel_coverage         0.882
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.993
_reflns_number_gt                22137
_reflns_number_total             24689
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b01124_si_002.cif
_cod_data_source_block           181128_hugh_5_46_3_0m
_cod_database_code               4128933
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.829
_shelx_estimated_absorpt_t_min   0.713
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups, All N(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C53-C54 \\sim C53-C54A
 with sigma of 0.02
 C55-C57 \\sim C55A-C57
 with sigma of 0.02
 C55-C54 \\sim C55A-C54A
 with sigma of 0.02
 C55-C56 \\sim C55A-C56A
 with sigma of 0.02
 C53-C55 \\sim C53-C55A
 with sigma of 0.04
 C57-C54 \\sim C57-C54A
 with sigma of 0.04
 C57-C56 \\sim C57-C56A
 with sigma of 0.04
 C54-C56 \\sim C54A-C56A
 with sigma of 0.04
 N3-C58 \\sim N3-C58A
 with sigma of 0.02
 O3-C58 \\sim O3A-C58A
 with sigma of 0.02
 C55-C57 \\sim C55-C57A
 with sigma of 0.02
 C57-C58 \\sim C57A-C58A
 with sigma of 0.02
 C57-C55A \\sim C57A-C55A
 with sigma of 0.02
 C57-C56A \\sim C57A-C56A
 with sigma of 0.02
 N3-O3 \\sim N3-O3A
 with sigma of 0.04
 N3-C57 \\sim N3-C57A
 with sigma of 0.04
 O3-C57 \\sim O3A-C57A
 with sigma of 0.04
 C55-C58 \\sim C55-C58A
 with sigma of 0.04
 C58-C55A \\sim C58A-C55A
 with sigma of 0.04
 C58-C56A \\sim C58A-C56A
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
C53 \\sim O3 \\sim C54 \\sim C55 \\sim C56 \\sim C57 \\sim C58 \\sim O3A \\sim
C54A \\sim C55A \\sim C56A \\sim C57A \\sim C58A: within 3.8A with sigma of
0.01 and sigma for terminal atoms of 0.02
4. Others
 Sof(H3B)=Sof(O3A)=Sof(C54A)=Sof(C55A)=Sof(H55A)=Sof(C56A)=Sof(H56D)=Sof(H56E)=
 Sof(H56F)=Sof(C57A)=Sof(H57C)=Sof(H57D)=Sof(C58A)=1-FVAR(1)
 Sof(H3A)=Sof(O3)=Sof(C54)=Sof(C55)=Sof(H55)=Sof(C56)=Sof(H56A)=Sof(H56B)=
 Sof(H56C)=Sof(C57)=Sof(H57A)=Sof(H57B)=Sof(C58)=FVAR(1)
5.a Riding coordinates:
 N3(H3B)
5.b Ternary CH refined with riding coordinates:
 C22(H22), C55(H55), C55A(H55A), C88(H88), C121(H121)
5.c Secondary CH2 refined with riding coordinates:
 C24(H24A,H24B), C57(H57A,H57B), C57A(H57C,H57D), C90(H90A,H90B), C123(H12D,
 H12E)
5.d Aromatic/amide H refined with riding coordinates:
 N1(H1), C9(H9), C10(H10), C11(H11), C12(H12), C13(H13), C15(H15), C16(H16),
 C17(H17), C18(H18), C19(H19), C30(H30), C31(H31), C32(H32), C33(H33), N3(H3A),
 C42(H42), C43(H43), C44(H44), C45(H45), C46(H46), C48(H48), C49(H49), C50(H50),
  C51(H51), C52(H52), C63(H63), C64(H64), C65(H65), C66(H66), N5(H5), C75(H75),
 C76(H76), C77(H77), C78(H78), C79(H79), C81(H81), C82(H82), C83(H83), C84(H84),
  C85(H85), C96(H96), C97(H97), C98(H98), C99(H99), N7(H7), C108(H108),
 C109(H109), C110(H110), C111(H111), C112(H112), C114(H114), C115(H115),
 C116(H116), C117(H117), C118(H118), C129(H129), C130(H130), C131(H131),
 C132(H132)
5.e Idealised Me refined as rotating group:
 C2(H2A,H2B,H2C), C3(H3C,H3D,H3E), C4(H4A,H4B,H4C), C5(H5A,H5B,H5C), C6(H6A,
 H6B,H6C), C23(H23A,H23B,H23C), C27(H27A,H27B,H27C), C28(H28A,H28B,H28C),
 C35(H35A,H35B,H35C), C36(H36A,H36B,H36C), C37(H37A,H37B,H37C), C38(H38A,H38B,
 H38C), C39(H39A,H39B,H39C), C60(H60A,H60B,H60C), C61(H61A,H61B,H61C), C56(H56A,
 H56B,H56C), C56A(H56D,H56E,H56F), C68(H68A,H68B,H68C), C69(H69A,H69B,H69C),
 C70(H70A,H70B,H70C), C71(H71A,H71B,H71C), C72(H72A,H72B,H72C), C89(H89A,H89B,
 H89C), C93(H93A,H93B,H93C), C94(H94A,H94B,H94C), C101(H10A,H10B,H10C),
 C102(H10D,H10E,H10F), C103(H10G,H10H,H10I), C104(H10J,H10K,H10L), C105(H10M,
 H10N,H10O), C122(H12A,H12B,H12C), C126(H12F,H12G,H12H), C127(H12I,H12J,H12K)
;
_shelx_res_checksum              65865
_shelx_hkl_checksum              45019
_olex2_submission_special_instructions 'No special instructions were received'