Enantioselective synthesis of trifluoromethyl substituted piperidines with multiple stereogenic centers via hydrogenation of pyridinium hydrochlorides
Chen, Mu-Wang; Ye, Zhi-Shi; Chen, Zhang-Pei; Wu, Bo; Zhou, Yong-Gui; Organic Chemistry Frontiers 2 (2015) 586–; doi:10.1039/C5QO00069F

data_1553122
_publ_section_title
;
 Enantioselective synthesis of trifluoromethyl substituted piperidines
 with multiple stereogenic centers via hydrogenation of pyridinium
 hydrochlorides
;
_journal_issue                   5
_journal_name_full               'Organic Chemistry Frontiers'
_journal_page_first              586
_journal_paper_doi               10.1039/C5QO00069F
_journal_volume                  2
_journal_year                    2015
_chemical_absolute_configuration ad
_chemical_formula_sum            'C19 H20 F3 N'
_chemical_formula_weight         319.36
_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
_audit_creation_method           SHELXL-2013
_audit_update_record
;
2014-06-18 deposited with the CCDC.
2015-03-31 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 114.770(2)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   10.4422(3)
_cell_length_b                   33.2582(10)
_cell_length_c                   10.4466(3)
_cell_measurement_reflns_used    4239
_cell_measurement_temperature    296(2)
_cell_measurement_theta_max      68.07
_cell_measurement_theta_min      2.66
_cell_volume                     3294.20(17)
_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-2013 (Sheldrick, 2013)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_diffrn_ambient_temperature      296(2)
_diffrn_measured_fraction_theta_full 0.870
_diffrn_measured_fraction_theta_max 0.924
_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  0.0574
_diffrn_reflns_av_unetI/netI     0.0951
_diffrn_reflns_Laue_measured_fraction_full 0.870
_diffrn_reflns_Laue_measured_fraction_max 0.924
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       39
_diffrn_reflns_limit_k_min       -39
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            20088
_diffrn_reflns_point_group_measured_fraction_full 0.805
_diffrn_reflns_point_group_measured_fraction_max 0.855
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         64.999
_diffrn_reflns_theta_min         2.657
_exptl_absorpt_coefficient_mu    0.823
_exptl_absorpt_correction_T_max  0.7532
_exptl_absorpt_correction_T_min  0.4003
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   sadabs
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.288
_exptl_crystal_F_000             1344
_exptl_crystal_size_max          0.200
_exptl_crystal_size_mid          0.100
_exptl_crystal_size_min          0.020
_refine_diff_density_max         0.276
_refine_diff_density_min         -0.226
_refine_diff_density_rms         0.058
_refine_ls_abs_structure_details
; 
 Flack x determined using 1677 quotients [(I+)-(I-)]/[(I+)+(I-)] 
 (Parsons and Flack (2004), Acta Cryst. A60, s61). 
;
_refine_ls_abs_structure_Flack   0.10(12)
_refine_ls_extinction_coef       0.0012(2)
_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   1.028
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     834
_refine_ls_number_reflns         9612
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.028
_refine_ls_R_factor_all          0.1075
_refine_ls_R_factor_gt           0.0715
_refine_ls_shift/su_max          0.057
_refine_ls_shift/su_mean         0.006
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1550P)^2^+0.0971P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2153
_refine_ls_wR_factor_ref         0.2857
_reflns_Friedel_coverage         0.816
_reflns_Friedel_fraction_full    0.737
_reflns_Friedel_fraction_max     0.784
_reflns_number_gt                4284
_reflns_number_total             9612
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c5qo00069f2.cif
_cod_data_source_block           cu_dm14047_0m
_cod_original_sg_symbol_H-M      'P 21'
_cod_database_code               1553122
_shelx_estimated_absorpt_t_min   0.853
_shelx_estimated_absorpt_t_max   0.984
_shelxl_version_number           2013-4
_shelx_res_checksum              67167
_shelx_hkl_checksum              4981