Iron-Catalyzed Highly Enantioselective Hydrosilylation of Unactivated Terminal Alkenes.
Cheng, Biao; Liu, Wenbo; Lu, Zhan; Journal of the American Chemical Society 140 (2018) 5014–5017; doi:10.1021/jacs.8b01638

data_4132109
_publ_section_title
;
 Iron-Catalyzed Highly Enantioselective Hydrosilylation of Unactivated
 Terminal Alkenes.
;
_journal_issue                   15
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              5014
_journal_page_last               5017
_journal_paper_doi               10.1021/jacs.8b01638
_journal_volume                  140
_journal_year                    2018
_chemical_absolute_configuration rmad
_chemical_formula_moiety         'C46 H43 Cl2 Fe N3 O2'
_chemical_formula_sum            'C46 H43 Cl2 Fe N3 O2'
_chemical_formula_weight         796.58
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2017-12-23
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.3630(4)
_cell_length_b                   19.5669(7)
_cell_length_c                   20.1438(7)
_cell_measurement_reflns_used    21067
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      29.3987
_cell_measurement_theta_min      2.8575
_cell_volume                     4084.6(3)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.11 (release 16-05-2011 CrysAlis171 .NET)
(compiled May 16 2011,17:55:39)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.11 (release 16-05-2011 CrysAlis171 .NET)
(compiled May 16 2011,17:55:39)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.11 (release 16-05-2011 CrysAlis171 .NET)
(compiled May 16 2011,17:55:39)
;
_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      293.15
_diffrn_detector_area_resol_mean 10.3592
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_details
;
  1 omega  -16.00   84.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       11.7808   77.0000  -30.0000 100

  2 omega  -10.00   87.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       11.7808   38.0000 -120.0000 97

  3 omega  -53.00   45.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       11.7808  -77.0000   90.0000 98

  4 omega  -87.00   15.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      -11.4683  -38.0000 -180.0000 102

  5 omega  -90.00  -17.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      -11.4683  157.0000  -59.0000 73

  6 omega  -66.00    7.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      -11.4683  120.0000   69.0000 73

  7 omega  -15.00   88.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       11.7808   38.0000 -180.0000 103

  8 omega   14.00   66.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       11.7808 -120.0000  -14.0000 52

  9 omega  -67.00   45.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       11.7808  -77.0000 -120.0000 112

 10 omega  -64.00  -33.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       11.7808  154.0000 -133.0000 31
;
_diffrn_measurement_device_type  'Xcalibur, Atlas, Gemini ultra'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0185992000
_diffrn_orient_matrix_UB_12      -0.0135879000
_diffrn_orient_matrix_UB_13      0.0312293000
_diffrn_orient_matrix_UB_21      -0.0209896000
_diffrn_orient_matrix_UB_22      0.0303981000
_diffrn_orient_matrix_UB_23      0.0158115000
_diffrn_orient_matrix_UB_31      -0.0624526000
_diffrn_orient_matrix_UB_32      -0.0142647000
_diffrn_orient_matrix_UB_33      0.0039840000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0522
_diffrn_reflns_av_unetI/netI     0.0223
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            78236
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.348
_diffrn_reflns_theta_min         2.863
_diffrn_source                   'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.541
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.86253
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.11 (release 16-05-2011 CrysAlis171 .NET)
(compiled May 16 2011,17:55:39)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'dark red'
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.295
_exptl_crystal_description       block
_exptl_crystal_F_000             1664
_exptl_crystal_size_max          0.48
_exptl_crystal_size_mid          0.46
_exptl_crystal_size_min          0.38
_refine_diff_density_max         0.259
_refine_diff_density_min         -0.242
_refine_diff_density_rms         0.037
_refine_ls_abs_structure_details
;
 Flack x determined using 2620 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.021(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.029
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     491
_refine_ls_number_reflns         7475
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.029
_refine_ls_R_factor_all          0.0486
_refine_ls_R_factor_gt           0.0377
_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^)+(0.0370P)^2^+1.9083P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0860
_refine_ls_wR_factor_ref         0.0943
_reflns_Friedel_coverage         0.789
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.999
_reflns_number_gt                6449
_reflns_number_total             7475
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b01638_si_002.cif
_cod_data_source_block           171222_cb12304_meoh
_cod_database_code               4132109
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'c h o N Fe Cl'
_shelx_estimated_absorpt_t_max   0.821
_shelx_estimated_absorpt_t_min   0.781
_reflns_odcompleteness_completeness 99.70
_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
2.a Ternary CH refined with riding coordinates:
 C15(H15), C16(H16), C19(H19), C33(H33)
2.b Secondary CH2 refined with riding coordinates:
 C14(H14A,H14B)
2.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C4(H4), C9(H9), C10(H10), C11(H11), C21(H21), C22(H22), C23(H23),
 C24(H24), C25(H25), C27(H27), C28(H28), C29(H29), C30(H30), C31(H31), C35(H35),
  C36(H36), C37(H37), C38(H38), C39(H39), C41(H41), C42(H42), C43(H43),
 C44(H44), C45(H45)
2.d Idealised Me refined as rotating group:
 C17(H17A,H17B,H17C), C18(H18A,H18B,H18C), C32(H32A,H32B,H32C), C46(H46A,H46B,
 H46C)
;
_shelx_res_checksum              91100
_shelx_hkl_checksum              61574
_olex2_submission_special_instructions 'No special instructions were received'