Enantioselective Phenolic α-Oxidation Using H<sub>2</sub>O<sub>2</sub> via an Unusual Double Dearomatization Mechanism.
McLaughlin, Michael F.; Massolo, Elisabetta; Liu, Shubin; Johnson, Jeffrey S.; Journal of the American Chemical Society 141 (2019) 2645–2651; doi:10.1021/jacs.8b13006

data_4128169
_publ_section_title
;
 Enantioselective Phenolic \a-Oxidation Using H<sub>2</sub>O<sub>2</sub>
 via an Unusual Double Dearomatization Mechanism.
;
_journal_issue                   6
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              2645
_journal_page_last               2651
_journal_paper_doi               10.1021/jacs.8b13006
_journal_volume                  141
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C18 H20 O4'
_chemical_formula_sum            'C18 H20 O4'
_chemical_formula_weight         300.34
_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'
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-05-25
_audit_creation_method
;
Olex2 1.2
(compiled 2018.04.26 svn.r3504 for OlexSys, GUI svn.r5492)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.7102(2)
_cell_length_b                   12.1090(4)
_cell_length_c                   15.8056(5)
_cell_measurement_reflns_used    9902
_cell_measurement_temperature    100.0
_cell_measurement_theta_max      66.61
_cell_measurement_theta_min      5.60
_cell_volume                     1475.66(8)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_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      100.0
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_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  0.0185
_diffrn_reflns_av_unetI/netI     0.0119
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            12825
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        66.605
_diffrn_reflns_theta_max         66.605
_diffrn_reflns_theta_min         4.600
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.772
_exptl_absorpt_correction_T_max  0.9230
_exptl_absorpt_correction_T_min  0.7933
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.0454 before and 0.0292 after correction. The Ratio of minimum to maximum transmission is 0.8595. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.352
_exptl_crystal_description       block
_exptl_crystal_F_000             640
_exptl_crystal_size_max          0.451
_exptl_crystal_size_mid          0.241
_exptl_crystal_size_min          0.134
_refine_diff_density_max         0.205
_refine_diff_density_min         -0.187
_refine_diff_density_rms         0.046
_refine_ls_abs_structure_details
;
 Flack x determined using 1068 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.03(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.932
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     203
_refine_ls_number_reflns         2599
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      0.932
_refine_ls_R_factor_all          0.0284
_refine_ls_R_factor_gt           0.0283
_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^)+(0.1000P)^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         0.0935
_reflns_Friedel_coverage         0.713
_reflns_Friedel_fraction_full    0.998
_reflns_Friedel_fraction_max     0.998
_reflns_number_gt                2587
_reflns_number_total             2599
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b13006_si_001.cif
_cod_data_source_block           mfm_dimethyldimer_1_5_24
_cod_database_code               4128169
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.904
_shelx_estimated_absorpt_t_min   0.722
_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:
 C9(H9), C10(H10), C11(H11)
2.b Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C18(H18A,H18B)
2.c Aromatic/amide H refined with riding coordinates:
 C8(H8)
2.d Idealised Me refined as rotating group:
 C5(H5A,H5B,H5C), C7(H7A,H7B,H7C), C13(H13A,H13B,H13C), C15(H15A,H15B,H15C)
;
_shelx_res_checksum              68117
_shelx_hkl_checksum              86247
_olex2_submission_special_instructions 'No special instructions were received'