Highly Enantioselective Organocatalytic Oxidative Kinetic Resolution of Secondary Alcohols Using Chiral Alkoxyamines as Precatalysts: Catalyst Structure, Active Species, and Substrate Scope.
Murakami, Keiichi; Sasano, Yusuke; Tomizawa, Masaki; Shibuya, Masatoshi; Kwon, Eunsang; Iwabuchi, Yoshiharu; Journal of the American Chemical Society  (2014) 141205132142002–; doi:10.1021/ja509766f

data_4123049
_publ_section_title
;
 Highly Enantioselective Organocatalytic Oxidative Kinetic Resolution of
 Secondary Alcohols Using Chiral Alkoxyamines as Precatalysts: Catalyst
 Structure, Active Species, and Substrate Scope.
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              141205132142002
_journal_paper_doi               10.1021/ja509766f
_journal_year                    2014
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C27 H32 Br N O2'
_chemical_formula_sum            'C27 H32 Br N O2'
_chemical_formula_weight         482.46
_space_group_IT_number           4
_symmetry_cell_setting           monoclinic
_symmetry_Int_Tables_number      4
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_cell_angle_alpha                90.0000
_cell_angle_beta                 90.331(6)
_cell_angle_gamma                90.0000
_cell_formula_units_Z            4
_cell_length_a                   8.2270(9)
_cell_length_b                   26.921(3)
_cell_length_c                   10.8369(11)
_cell_measurement_reflns_used    22317
_cell_measurement_temperature    150
_cell_measurement_theta_max      27.60
_cell_measurement_theta_min      3.00
_cell_volume                     2400.1(4)
_computing_cell_refinement       'CrystalClear-SM Auto 2.0 r15'
_computing_data_collection       'CrystalClear-SM Auto 2.0 r15 (Rigaku, 2011)'
_computing_data_reduction        'CrystalClear-SM Auto 2.0 r15'
_computing_molecular_graphics    'CrystalStructure 4.0'
_computing_publication_material  'CrystalStructure 4.0 (Rigaku, 2010)'
_computing_structure_refinement  'SHELXL97 (Sheldrick, 2008)'
_computing_structure_solution    'SHELXS97 (Sheldrick, 2008)'
_diffrn_ambient_temperature      150
_diffrn_detector_area_resol_mean 6.827
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Rigaku XtaLAB mini'
_diffrn_measurement_method       \w
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71075
_diffrn_reflns_av_R_equivalents  0.0470
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       34
_diffrn_reflns_limit_k_min       -34
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            23440
_diffrn_reflns_theta_full        27.48
_diffrn_reflns_theta_max         27.48
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.741
_exptl_absorpt_correction_T_max  0.706
_exptl_absorpt_correction_T_min  0.546
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'REQAB (Rigaku, 1998)'
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.335
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       platelet
_exptl_crystal_F_000             1008.00
_exptl_crystal_size_max          0.400
_exptl_crystal_size_mid          0.200
_exptl_crystal_size_min          0.200
_refine_diff_density_max         1.070
_refine_diff_density_min         -0.470
_refine_ls_abs_structure_details
'Flack, H. D. (1983), Acta Cryst. A39, 876-881.  5335 Friedel Pairs'
_refine_ls_abs_structure_Flack   0.055(9)
_refine_ls_extinction_coef       0.0062(4)
_refine_ls_extinction_method     SHELXL
_refine_ls_goodness_of_fit_ref   1.117
_refine_ls_hydrogen_treatment    constr
_refine_ls_number_parameters     561
_refine_ls_number_reflns         10946
_refine_ls_number_restraints     1
_refine_ls_R_factor_gt           0.0581
_refine_ls_shift/su_max          0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w = 1/[\s^2^(Fo^2^)+(0.0160P)^2^+4.2712P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_ref         0.1305
_reflns_number_gt                9445
_reflns_number_total             10946
_reflns_threshold_expression     F^2^>2.0\s(F^2^)
_cod_data_source_file            ja509766f_si_002.cif
_cod_data_source_block           01
_cod_original_cell_volume        2400.1(5)
_cod_database_code               4123049