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_4132712
_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         'C26 H35 N O3'
_chemical_formula_sum            'C26 H35 N O3'
_chemical_formula_weight         409.55
_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
_audit_creation_date             2017-10-10
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                90
_cell_angle_beta                 101.860(4)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   6.1268(2)
_cell_length_b                   13.2115(5)
_cell_length_c                   14.7663(5)
_cell_measurement_reflns_used    4231
_cell_measurement_temperature    298
_cell_measurement_theta_max      28.2420
_cell_measurement_theta_min      3.7200
_cell_volume                     1169.73(7)
_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_temperature      298
_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     43.00  78.00   1.00   30.00    --   18.47-129.00-138.00   35
  2  \w    -22.00  90.00   1.00   30.00    --   18.47  19.00-120.00  112
  3  \w     17.00  91.00   1.00   30.00    --   18.47  37.00 120.00   74
  4  \w      6.00  73.00   1.00   30.00    --   18.63  57.00 -60.00   67
  5  \w    -79.00 -14.00   1.00   30.00    --  -19.56 128.00 -64.00   65
  6  \w    -65.00 -15.00   1.00   30.00    --  -19.56 -57.00  30.00   50
;
_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      -0.0046344000
_diffrn_orient_matrix_UB_12      0.0524190000
_diffrn_orient_matrix_UB_13      0.0097680000
_diffrn_orient_matrix_UB_21      0.0202576000
_diffrn_orient_matrix_UB_22      -0.0108355000
_diffrn_orient_matrix_UB_23      0.0480578000
_diffrn_orient_matrix_UB_31      0.1164649000
_diffrn_orient_matrix_UB_32      0.0039858000
_diffrn_orient_matrix_UB_33      0.0022940000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0160
_diffrn_reflns_av_unetI/netI     0.0216
_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       -11
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            8178
_diffrn_reflns_point_group_measured_fraction_full 0.874
_diffrn_reflns_point_group_measured_fraction_max 0.874
_diffrn_reflns_theta_full        25.008
_diffrn_reflns_theta_max         25.008
_diffrn_reflns_theta_min         3.084
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.075
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.74599
_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    1.163
_exptl_crystal_description       block
_exptl_crystal_F_000             444
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.28
_exptl_crystal_size_min          0.25
_refine_diff_density_max         0.141
_refine_diff_density_min         -0.149
_refine_diff_density_rms         0.029
_refine_ls_abs_structure_details
;
 Flack x determined using 1195 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.2(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.048
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     274
_refine_ls_number_reflns         3633
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.047
_refine_ls_R_factor_all          0.0400
_refine_ls_R_factor_gt           0.0355
_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^)+(0.0480P)^2^+0.0820P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0867
_refine_ls_wR_factor_ref         0.0908
_reflns_Friedel_coverage         0.672
_reflns_Friedel_fraction_full    0.738
_reflns_Friedel_fraction_max     0.738
_reflns_number_gt                3313
_reflns_number_total             3633
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b05753_si_002.cif
_cod_data_source_block           p171010a1
_cod_original_cell_volume        1169.72(8)
_cod_database_code               4132712
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C H O N'
_chemical_oxdiff_usercomment     HG-1
_shelx_estimated_absorpt_t_max   0.982
_shelx_estimated_absorpt_t_min   0.978
_reflns_odcompleteness_completeness 99.84
_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, All O(H) groups
2.a Ternary CH refined with riding coordinates:
 C12(H12), C15(H15), C16(H16), C22(H22), C8(H8)
2.b Secondary CH2 refined with riding coordinates:
 C13(H13A,H13B), C9(H9A,H9B), C10(H10A,H10B), C17(H17A,H17B), C26(H26A,H26B),
 C19(H19A,H19B), C20(H20A,H20B), C18(H18A,H18B), C25(H25A,H25B)
2.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3A), C6(H6), C4(H4), C5(H5)
2.d Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C23(H23A,H23B,H23C)
2.e Idealised tetrahedral OH refined as rotating group:
 O3(H3)
;
_olex2_date_sample_data_collection 2017-10-10
_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 1.286
_oxdiff_exptl_absorpt_empirical_full_min 0.703