An Enantioselective Oxidative C-H/C-H Cross-Coupling Reaction: Highly Efficient Method To Prepare Planar Chiral Ferrocenes.
Gao, De-Wei; Gu, Qing; You, Shu-Li; Journal of the American Chemical Society 138 (2016) 2544–2547; doi:10.1021/jacs.6b00127

data_4130096
_publ_section_title
;
 An Enantioselective Oxidative C-H/C-H Cross-Coupling Reaction: Highly
 Efficient Method To Prepare Planar Chiral Ferrocenes.
;
_journal_issue                   8
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              2544
_journal_page_last               2547
_journal_paper_doi               10.1021/jacs.6b00127
_journal_volume                  138
_journal_year                    2016
_chemical_absolute_configuration rmad
_chemical_formula_moiety         'C23 H22 Cl Fe N S'
_chemical_formula_sum            'C23 H22 Cl Fe N S'
_chemical_formula_weight         435.78
_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   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2015-05-29
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_cell_angle_alpha                90.00
_cell_angle_beta                 95.788(10)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   6.883(4)
_cell_length_b                   10.729(6)
_cell_length_c                   27.388(15)
_cell_measurement_reflns_used    1177
_cell_measurement_temperature    130
_cell_measurement_theta_max      24.12
_cell_measurement_theta_min      2.42
_cell_volume                     2012(2)
_computing_cell_refinement       'SAINT v7.68A (Bruker, 2009)'
_computing_data_reduction        'SAINT v7.68A (Bruker, 2009)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XH (Sheldrick, 2008)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      130
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0000
_diffrn_reflns_av_unetI/netI     0.0539
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       0
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       0
_diffrn_reflns_number            4212
_diffrn_reflns_theta_full        25.99
_diffrn_reflns_theta_max         25.99
_diffrn_reflns_theta_min         0.75
_diffrn_source                   'fine-focus sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.993
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.6339
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
 TWINABS-2008/4 (Bruker,2010) was used for absorption correction.
 
For component 1:
 wR2(int) was 0.0637 before and 0.0579 after correction.
 The Ratio of minimum to maximum transmission is 0.85.
 The \l/2 correction factor is Not present

Final HKLF 4 output contains 17324 reflections, Rint = 0.0634
 (7358 with I > 3sig(I), Rint = 0.0487)
;
_exptl_crystal_colour            red
_exptl_crystal_density_diffrn    1.438
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       BLOCK
_exptl_crystal_F_000             904
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.472
_refine_diff_density_min         -0.666
_refine_diff_density_rms         0.078
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.08(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.147
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     492
_refine_ls_number_reflns         4212
_refine_ls_number_restraints     349
_refine_ls_restrained_S_all      1.116
_refine_ls_R_factor_all          0.0462
_refine_ls_R_factor_gt           0.0396
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0298P)^2^+1.7508P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0927
_refine_ls_wR_factor_ref         0.0954
_reflns_number_gt                3791
_reflns_number_total             4212
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja6b00127_si_003.cif
_cod_data_source_block           dm15445
_cod_original_cell_volume        2012.3(19)
_cod_database_code               4130096
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.5461(12) 0.4539(12)
2. 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
3. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 1.7A with sigma of 0.04 and sigma
for terminal atoms of 0.08
Uanis(C33) \\sim Ueq, Uanis(C24) \\sim Ueq, Uanis(C35) \\sim Ueq, Uanis(C42)
\\sim Ueq, Uanis(C41) \\sim Ueq, Uanis(C5) \\sim Ueq, Uanis(C4) \\sim Ueq,
Uanis(C3) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
4.a Ternary CH refined with riding coordinates:
 C5(H5)
4.b Secondary CH2 refined with riding coordinates:
 C21(H21A,H21B), C44(H44A,H44B)
4.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C6(H6), C7(H7), C8(H8), C12(H12), C13(H13),
 C16(H16), C17(H17), C19(H19), C20(H20), C24(H24), C25(H25), C26(H26), C27(H27),
  C28(H28), C29(H29), C30(H30), C31(H31), C35(H35), C36(H36), C39(H39),
 C40(H40), C42(H42), C43(H43)
4.d Idealised Me refined as rotating group:
 C22(H22A,H22B,H22C), C23(H23A,H23B,H23C), C45(H45A,H45B,H45C), C46(H46A,H46B,
 H46C)
;
_olex2_submission_special_instructions 'No special instructions were received'