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_4133051
_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         'C6 H5 O3 S, C11 H17 N4 O'
_chemical_formula_sum            'C17 H22 N4 O4 S'
_chemical_formula_weight         378.44
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2017-11-06
_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                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   9.204(3)
_cell_length_b                   10.736(3)
_cell_length_c                   37.751(9)
_cell_measurement_reflns_used    9958
_cell_measurement_temperature    100
_cell_measurement_theta_max      30.326
_cell_measurement_theta_min      3.335
_cell_volume                     3730.3(18)
_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, 2008)'
_computing_structure_solution    'XT (Sheldrick, 2015a)'
_diffrn_ambient_temperature      100.0
_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 0.994
_diffrn_measured_fraction_theta_max 0.995
_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  0.0572
_diffrn_reflns_av_unetI/netI     0.0286
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       53
_diffrn_reflns_limit_l_min       -53
_diffrn_reflns_number            80903
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         30.537
_diffrn_reflns_theta_min         3.335
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_exptl_absorpt_coefficient_mu    0.204
_exptl_absorpt_correction_T_max  0.7461
_exptl_absorpt_correction_T_min  0.6340
_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    1.348
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plank
_exptl_crystal_F_000             1600
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.576
_refine_diff_density_min         -0.345
_refine_diff_density_rms         0.060
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.093
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     264
_refine_ls_number_reflns         5675
_refine_ls_number_restraints     18
_refine_ls_restrained_S_all      1.102
_refine_ls_R_factor_all          0.0569
_refine_ls_R_factor_gt           0.0478
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0481P)^2^+2.6479P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1148
_refine_ls_wR_factor_ref         0.1191
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4903
_reflns_number_total             5675
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b08145_si_002.cif
_cod_data_source_block           stahl234
_cod_original_cell_volume        3730.1(17)
_cod_database_code               4133051
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.992
_shelx_estimated_absorpt_t_min   0.960
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 N1-H1B \\sim N1-H1A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C14) \\sim Ueq, Uanis(C13A) \\sim Ueq: with sigma of 0.004 and sigma for
terminal atoms of 0.008
4. Same fragment restrains
{C11, C12, C13A, C14A} sigma for 1-2: 0.01, 1-3: 0.02
as
{C11, C12, C13, C14}
5. Others
 Sof(H12A)=Sof(C13A)=Sof(H13D)=Sof(H13E)=Sof(H13F)=Sof(C14A)=Sof(H14D)=
 Sof(H14E)=Sof(H14F)=1-FVAR(1)
 Sof(H12)=Sof(C13)=Sof(H13A)=Sof(H13B)=Sof(H13C)=Sof(C14)=Sof(H14A)=Sof(H14B)=
 Sof(H14C)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 C9(H9), C12(H12A), C12(H12), C16(H16)
6.b Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C8(H8A,H8B), C15(H15A,H15B)
6.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C6(H6)
6.d Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C13A(H13D,H13E,H13F), C14A(H14D,
 H14E,H14F)
;
_shelx_res_checksum              15502
_shelx_hkl_checksum              2663
_olex2_submission_special_instructions 'No special instructions were received'