Pd-catalyzed asymmetric hydrogenation of fluorinated aromatic pyrazol-5-ols via capture of active tautomers
Chen, Zhang-Pei; Chen, Mu-Wang; Shi, Lei; Yu, Chang-Bin; Zhou, Yong-Gui; Chem. Sci. 6 (2015) 3415–; doi:10.1039/C5SC00835B

data_1518948
_publ_section_title
;
 Pd-catalyzed asymmetric hydrogenation of fluorinated aromatic
 pyrazol-5-ols via capture of active tautomers
;
_journal_issue                   6
_journal_name_full               'Chem. Sci.'
_journal_page_first              3415
_journal_paper_doi               10.1039/C5SC00835B
_journal_volume                  6
_journal_year                    2015
_chemical_absolute_configuration ad
_chemical_formula_sum            'C17 H15 F3 N2 O'
_chemical_formula_weight         320.31
_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
_audit_creation_method           SHELXL-2014
_audit_update_record
;
2014-12-22 deposited with the CCDC.
2015-03-31 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   5.74670(10)
_cell_length_b                   9.45740(10)
_cell_length_c                   27.5934(4)
_cell_measurement_reflns_used    4266
_cell_measurement_temperature    296(2)
_cell_measurement_theta_max      68.73
_cell_measurement_theta_min      4.94
_cell_volume                     1499.67(4)
_computing_cell_refinement       'Bruker SAINT'
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'Bruker SAINT'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'
_computing_structure_refinement  'SHELXL-2014 (Sheldrick, 2014)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_diffrn_ambient_temperature      296(2)
_diffrn_measured_fraction_theta_full 0.986
_diffrn_measured_fraction_theta_max 0.969
_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  0.0629
_diffrn_reflns_av_unetI/netI     0.0475
_diffrn_reflns_Laue_measured_fraction_full 0.986
_diffrn_reflns_Laue_measured_fraction_max 0.969
_diffrn_reflns_limit_h_max       5
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            10146
_diffrn_reflns_point_group_measured_fraction_full 0.985
_diffrn_reflns_point_group_measured_fraction_max 0.963
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         69.570
_diffrn_reflns_theta_min         4.943
_exptl_absorpt_coefficient_mu    0.982
_exptl_absorpt_correction_T_max  0.7532
_exptl_absorpt_correction_T_min  0.4332
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   sadabs
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.419
_exptl_crystal_F_000             664
_exptl_crystal_size_max          0.250
_exptl_crystal_size_mid          0.030
_exptl_crystal_size_min          0.020
_refine_diff_density_max         0.330
_refine_diff_density_min         -0.290
_refine_diff_density_rms         0.043
_refine_ls_abs_structure_details
; 
 Flack x determined using 988 quotients [(I+)-(I-)]/[(I+)+(I-)] 
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259). 
;
_refine_ls_abs_structure_Flack   0.00(9)
_refine_ls_extinction_coef       0.0206(18)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     SHELXL
_refine_ls_goodness_of_fit_ref   1.036
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     209
_refine_ls_number_reflns         2707
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.036
_refine_ls_R_factor_all          0.0445
_refine_ls_R_factor_gt           0.0426
_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^)+(0.0732P)^2^+0.1986P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1187
_refine_ls_wR_factor_ref         0.1214
_reflns_Friedel_coverage         0.675
_reflns_Friedel_fraction_full    0.983
_reflns_Friedel_fraction_max     0.953
_reflns_number_gt                2549
_reflns_number_total             2707
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c5sc00835b2.cif
_cod_data_source_block           cu_dm14398_0m
_cod_depositor_comments
'Adding full bibliography for 1518946--1518948.cif.'
_cod_database_code               1518948
_shelx_estimated_absorpt_t_min   0.791
_shelx_estimated_absorpt_t_max   0.981
_shelxl_version_number           2014-3
_shelx_res_checksum              70009
_shelx_hkl_checksum              88827