Stereoselective α-Hydroxylation of Amides Using Oppolzer's Sultam as Chiral Auxiliary.
Zhang, Lumin; Zhu, Lili; Yang, Jun; Luo, Jisheng; Hong, Ran; The Journal of organic chemistry 81 (2016) 3890–3900; doi:10.1021/acs.joc.6b00068

data_4036624
_publ_section_title
;
 Stereoselective \a-Hydroxylation of Amides Using Oppolzer's Sultam as
 Chiral Auxiliary.
;
_journal_issue                   9
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              3890
_journal_page_last               3900
_journal_paper_doi               10.1021/acs.joc.6b00068
_journal_volume                  81
_journal_year                    2016
_chemical_absolute_configuration rmad
_chemical_formula_moiety         'C20 H27 N O5 S'
_chemical_formula_sum            'C20 H27 N O5 S'
_chemical_formula_weight         393.48
_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             2015-06-29
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_cell_angle_alpha                90
_cell_angle_beta                 104.481(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.5968(12)
_cell_length_b                   8.2171(9)
_cell_length_c                   21.456(2)
_cell_measurement_reflns_used    5077
_cell_measurement_temperature    296(2)
_cell_measurement_theta_max      28.38
_cell_measurement_theta_min      2.27
_cell_volume                     1979.6(4)
_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  'XL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      296.15
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_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  0.0265
_diffrn_reflns_av_unetI/netI     0.0331
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            13145
_diffrn_reflns_point_group_measured_fraction_full 0.801
_diffrn_reflns_point_group_measured_fraction_max 0.795
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.000
_diffrn_reflns_theta_min         1.814
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.194
_exptl_absorpt_correction_T_max  0.7461
_exptl_absorpt_correction_T_min  0.6686
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.0441 before and 0.0388 after correction.
The Ratio of minimum to maximum transmission is 0.8961.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.320
_exptl_crystal_description       block
_exptl_crystal_F_000             840
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.183
_refine_diff_density_min         -0.368
_refine_diff_density_rms         0.054
_refine_ls_abs_structure_details
;
 Flack x determined using 1656 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.06(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.006
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     495
_refine_ls_number_reflns         6203
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.006
_refine_ls_R_factor_all          0.0433
_refine_ls_R_factor_gt           0.0361
_refine_ls_shift/su_max          0.038
_refine_ls_shift/su_mean         0.002
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0664P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0910
_refine_ls_wR_factor_ref         0.0961
_reflns_Friedel_coverage         0.484
_reflns_Friedel_fraction_full    0.573
_reflns_Friedel_fraction_max     0.560
_reflns_number_gt                5501
_reflns_number_total             6203
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo6b00068_si_002.cif
_cod_data_source_block           mo_dm15514_0m
_cod_original_cell_volume        1979.7(4)
_cod_database_code               4036624
_shelxl_version_number           2014-3
_shelx_estimated_absorpt_t_max   0.971
_shelx_estimated_absorpt_t_min   0.953
_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:
 C5(H5), C7(H7), C12(H12), C25(H25), C27(H27), C32(H32)
2.b Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C3(H3A,H3B), C4(H4A,H4B), C6(H6A,H6B), C13(H13A,H13B), C21(H21A,
 H21B), C23(H23A,H23B), C24(H24A,H24B), C26(H26A,H26B), C33(H33A,H33B)
2.c Aromatic/amide H refined with riding coordinates:
 C15(H15), C16(H16), C17(H17), C19(H19), C35(H35), C36(H36), C37(H37), C39(H39)
2.d Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C20(H20A,H20B,H20C), C29(H29A,H29B,
 H29C), C30(H30A,H30B,H30C), C40(H40A,H40B,H40C)
2.e Idealised tetrahedral OH refined as rotating group:
 O4(H4), O9(H9)
;
_shelx_res_checksum              74721
_shelx_hkl_checksum              21821
_olex2_submission_special_instructions 'No special instructions were received'