Epimerization of Tertiary Carbon Centers via Reversible Radical Cleavage of Unactivated C(sp<sup>3</sup>)-H Bonds.
Wang, Yaxin; Hu, Xiafei; Morales-Rivera, Cristian A; Li, Guo-Xing; Huang, Xin; He, Gang; Liu, Peng; Chen, Gong; Journal of the American Chemical Society 140 (2018) 9678–9684; doi:10.1021/jacs.8b05753

data_4132709
_publ_section_title
;
 Epimerization of Tertiary Carbon Centers via Reversible Radical Cleavage
 of Unactivated C(sp<sup>3</sup>)-H Bonds.
;
_journal_issue                   30
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              9678
_journal_page_last               9684
_journal_paper_doi               10.1021/jacs.8b05753
_journal_volume                  140
_journal_year                    2018
_chemical_absolute_configuration R
_chemical_formula_moiety         'C35 H44 O4'
_chemical_formula_sum            'C35 H44 O4'
_chemical_formula_weight         528.70
_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     direct
_audit_creation_date             2018-02-01
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2017.08.10 svn.r3458 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                   6.3698(5)
_cell_length_b                   13.2280(12)
_cell_length_c                   34.571(2)
_cell_measurement_reflns_used    2403
_cell_measurement_temperature    120.00(10)
_cell_measurement_theta_max      27.1930
_cell_measurement_theta_min      3.3960
_cell_volume                     2912.9(4)
_computing_cell_refinement       'CrysAlisPro 1.171.39.29c (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.29c (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.29c (Rigaku OD, 2017)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XS (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      120.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.2116
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_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    -12.00  32.00   1.00   22.50    --   18.55  77.00   0.00   44
  2  \w     -7.00  88.00   1.00   22.50    --   18.55  77.00-120.00   95
  3  \w    -47.00  51.00   1.00   22.50    --  -19.56  77.00 120.00   98
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Single source at offset/far, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0144117000
_diffrn_orient_matrix_UB_12      0.0393562000
_diffrn_orient_matrix_UB_13      -0.0136937000
_diffrn_orient_matrix_UB_21      0.0176029000
_diffrn_orient_matrix_UB_22      0.0348251000
_diffrn_orient_matrix_UB_23      0.0152597000
_diffrn_orient_matrix_UB_31      0.1089530000
_diffrn_orient_matrix_UB_32      -0.0108291000
_diffrn_orient_matrix_UB_33      -0.0006383000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0652
_diffrn_reflns_av_unetI/netI     0.0938
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       41
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            11579
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.026
_diffrn_reflns_theta_max         25.026
_diffrn_reflns_theta_min         3.080
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.077
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.75862
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.29c (Rigaku Oxford Diffraction, 2017)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.206
_exptl_crystal_description       block
_exptl_crystal_F_000             1144
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.28
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.175
_refine_diff_density_min         -0.166
_refine_diff_density_rms         0.042
_refine_ls_abs_structure_details
;
 Flack x determined using 1135 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   1.4(10)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.034
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     355
_refine_ls_number_reflns         5142
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.034
_refine_ls_R_factor_all          0.0806
_refine_ls_R_factor_gt           0.0570
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0230P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0933
_refine_ls_wR_factor_ref         0.1045
_reflns_Friedel_coverage         0.727
_reflns_Friedel_fraction_full    0.996
_reflns_Friedel_fraction_max     0.996
_reflns_number_gt                4008
_reflns_number_total             5142
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b05753_si_005.cif
_cod_data_source_block           p180131c
_cod_database_code               4132709
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C H O'
_shelx_estimated_absorpt_t_max   0.985
_shelx_estimated_absorpt_t_min   0.977
_reflns_odcompleteness_completeness 99.74
_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:
 C27(H27), C22(H22), C18(H18), C13(H13), C10(H10), C19(H19), C8(H8)
2.b Secondary CH2 refined with riding coordinates:
 C20(H20A,H20B), C28(H28A,H28B), C16(H16A,H16B), C25(H25A,H25B), C21(H21A,
 H21B), C26(H26A,H26B), C11(H11A,H11B), C12(H12A,H12B), C17(H17A,H17B)
2.c Aromatic/amide H refined with riding coordinates:
 C35(H35), C33(H33), C34(H34), C32(H32), C4(H4), C31(H31), C1(H1), C3(H3),
 C5(H5), C2(H2)
2.d Idealised Me refined as rotating group:
 C24(H24A,H24B,H24C), C15(H15A,H15B,H15C), C9(H9A,H9B,H9C)
;
_olex2_date_sample_data_collection 2018-01-31
_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 1.422
_oxdiff_exptl_absorpt_empirical_full_min 0.738