Electrochemical Aminoxyl-Mediated α-Cyanation of Secondary Piperidines for Pharmaceutical Building Block Diversification.
Lennox, Alastair J. J.; Goes, Shannon L.; Webster, Matthew P.; Koolman, Hannes F.; Djuric, Stevan W.; Stahl, Shannon S.; Journal of the American Chemical Society 140 (2018) 11227–11231; doi:10.1021/jacs.8b08145

data_4133052
_publ_section_title
;
 Electrochemical Aminoxyl-Mediated \a-Cyanation of Secondary Piperidines
 for Pharmaceutical Building Block Diversification.
;
_journal_issue                   36
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              11227
_journal_page_last               11231
_journal_paper_doi               10.1021/jacs.8b08145
_journal_volume                  140
_journal_year                    2018
_chemical_formula_moiety         'Cl, C13 H13.5 F N2 O3, H2.5 O, C2 H4 O'
_chemical_formula_sum            'C15 H20 Cl F N2 O5'
_chemical_formula_weight         362.78
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2017-11-15
_audit_creation_method
;
Olex2 1.2-dev
(compiled 2017.10.03 svn.r3461 for OlexSys, GUI svn.r5395)
;
_cell_angle_alpha                90
_cell_angle_beta                 111.357(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   16.188(2)
_cell_length_b                   6.4618(8)
_cell_length_c                   16.639(2)
_cell_measurement_reflns_used    9985
_cell_measurement_temperature    100
_cell_measurement_theta_max      30.046
_cell_measurement_theta_min      2.630
_cell_volume                     1621.0(3)
_computing_cell_refinement       'APEX3 Ver. 2017.3-0 (Bruker-AXS, 2017)'
_computing_data_collection       'APEX3 Ver. 2017.3-0 (Bruker-AXS, 2017)'
_computing_data_reduction        'APEX3 Ver. 2017.3-0 (Bruker-AXS, 2017)'
_computing_molecular_graphics    'OLEX2 (Dolomanov et al., 2009)'
_computing_publication_material  'OLEX2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2015b)'
_computing_structure_solution    'XT (Sheldrick, 2015a)'
_diffrn_ambient_temperature      99.96
_diffrn_detector                 'charge-coupled device (CCD) area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'Bruker APEX II'
_diffrn_measured_fraction_theta_full 0.989
_diffrn_measured_fraction_theta_max 0.992
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker APEX II Quazar'
_diffrn_measurement_method       '0.5\% \w and 0.5\% \f scans'
_diffrn_radiation_collimation    'focusing mirrors'
_diffrn_radiation_detector       'Bruker APEX II'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0366
_diffrn_reflns_av_unetI/netI     0.0223
_diffrn_reflns_Laue_measured_fraction_full 0.989
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            36440
_diffrn_reflns_point_group_measured_fraction_full 0.989
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         30.052
_diffrn_reflns_theta_min         1.503
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_exptl_absorpt_coefficient_mu    0.275
_exptl_absorpt_correction_T_max  0.7460
_exptl_absorpt_correction_T_min  0.7156
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Krause et al., 2015) was used for absorption correction.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.487
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       needle
_exptl_crystal_F_000             760
_exptl_crystal_size_max          0.268
_exptl_crystal_size_mid          0.099
_exptl_crystal_size_min          0.042
_refine_diff_density_max         0.514
_refine_diff_density_min         -0.218
_refine_diff_density_rms         0.063
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.040
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     235
_refine_ls_number_reflns         4702
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.040
_refine_ls_R_factor_all          0.0422
_refine_ls_R_factor_gt           0.0373
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0561P)^2^+0.6954P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0986
_refine_ls_wR_factor_ref         0.1020
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4165
_reflns_number_total             4702
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b08145_si_003.cif
_cod_data_source_block           stahl235
_cod_original_cell_volume        1621.0(4)
_cod_database_code               4133052
_shelx_shelxl_version_number     2017/1
_shelx_estimated_absorpt_t_max   0.989
_shelx_estimated_absorpt_t_min   0.930
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, {H15A,H15B} of C15, {H14A,H14B} of C14, {H9A,H9B} of C9,
  {H10A,H10B} of C10, {H12A,H12B} of C12, All N(H,H) groups
 At 1.5 times of:
  All O(H,H) groups, {H3,H4B} of C15
2. Others
 Fixed Sof: H3(0.5) H4B(0.5)
3.a Ternary CH refined with riding coordinates:
 C8(H8), C11(H11)
3.b Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B), C10(H10A,H10B), C12(H12A,H12B), C14(H14A,H14B), C15(H15A,H15B)
3.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C4(H4), C5(H5)
;
_shelx_res_checksum              37868
_shelx_hkl_checksum              16368
_olex2_submission_special_instructions 'No special instructions were received'