Catalytic Kinetic Resolution of Disubstituted Piperidines by Enantioselective Acylation: Synthetic Utility and Mechanistic Insights.
Wanner, Benedikt; Kreituss, Imants; Gutierrez, Osvaldo; Kozlowski, Marisa C.; Bode, Jeffrey W.; Journal of the American Chemical Society 137 (2015) 11491–11497; doi:10.1021/jacs.5b07201

data_4129503
_publ_section_title
;
 Catalytic Kinetic Resolution of Disubstituted Piperidines by
 Enantioselective Acylation: Synthetic Utility and Mechanistic Insights.
;
_journal_issue                   35
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              11491
_journal_page_last               11497
_journal_paper_doi               10.1021/jacs.5b07201
_journal_volume                  137
_journal_year                    2015
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C20 H24 N2 O4 S'
_chemical_formula_sum            'C20 H24 N2 O4 S'
_chemical_formula_weight         388.47
_chemical_name_systematic
4-benzyl-2-ethyl-1-((4-nitrophenyl)sulfonyl)piperidine
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2015-01-27
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.8603(7)
_cell_length_b                   11.6145(9)
_cell_length_c                   18.4379(14)
_cell_measurement_reflns_used    9840
_cell_measurement_temperature    100.0(2)
_cell_measurement_theta_max      30.52
_cell_measurement_theta_min      2.21
_cell_volume                     1897.4(3)
_computing_cell_refinement       'Bruker SAINT'
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'Bruker SAINT'
_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    'XS (Sheldrick, 2008)'
_diffrn_ambient_temperature      100.0(2)
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 8.33
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.903
_diffrn_measured_fraction_theta_max 0.857
_diffrn_measurement_device       'kappa-stage diffractometer'
_diffrn_measurement_device_type  'Bruker Apex2 Duo (Mo)'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'focusing graphite'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0198
_diffrn_reflns_av_unetI/netI     0.0114
_diffrn_reflns_Laue_measured_fraction_full 0.903
_diffrn_reflns_Laue_measured_fraction_max 0.857
_diffrn_reflns_limit_h_max       5
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            32217
_diffrn_reflns_point_group_measured_fraction_full 0.907
_diffrn_reflns_point_group_measured_fraction_max 0.860
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.484
_diffrn_reflns_theta_min         2.072
_diffrn_source                   'sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.199
_exptl_absorpt_correction_T_max  0.7461
_exptl_absorpt_correction_T_min  0.7131
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.0404 before and 0.0377 after correction.
The Ratio of minimum to maximum transmission is 0.9558.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.360
_exptl_crystal_description       plate
_exptl_crystal_F_000             824
_exptl_crystal_size_max          0.28
_exptl_crystal_size_mid          0.24
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.214
_refine_diff_density_min         -0.263
_refine_diff_density_rms         0.033
_refine_ls_abs_structure_details
;
 Flack x determined using 1572 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.029(11)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.058
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     245
_refine_ls_number_reflns         3747
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.058
_refine_ls_R_factor_all          0.0241
_refine_ls_R_factor_gt           0.0232
_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^)+(0.0353P)^2^+0.3796P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0601
_refine_ls_wR_factor_ref         0.0607
_reflns_Friedel_coverage         0.760
_reflns_Friedel_fraction_full    0.912
_reflns_Friedel_fraction_max     0.864
_reflns_number_gt                3656
_reflns_number_total             3747
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja5b07201_si_002.cif
_cod_data_source_block           mo_jb200115_1_1_0m
_cod_database_code               4129503
_shelxl_version_number           2014/6
_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:
 C6(H6), C8(H8)
2.b Secondary CH2 refined with riding coordinates:
 C5(H5A,H5B), C7(H7A,H7B), C15(H15A,H15B), C16(H16A,H16B), C17(H17A,H17B)
2.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C10(H10), C11(H11), C13(H13), C14(H14), C19(H19),
 C20(H20)
2.d Idealised Me refined as rotating group:
 C18(H18A,H18B,H18C)
;
_shelx_res_checksum              45605
_shelx_hkl_checksum              50506
_olex2_submission_original_sample_id jb200115_1_1
_olex2_submission_special_instructions 'No special instructions were received'