Electrochemical Synthesis of Hindered Primary and Secondary Amines via Proton-Coupled Electron Transfer
Lehnherr, Dan; Lam, Yu-hong; Nicastri, Michael C.; Liu, Jinchu; Newman, Justin A.; Regalado, Erik L.; DiRocco, Daniel A.; Rovis, Tomislav; Journal of the American Chemical Society  (2019) –; doi:10.1021/jacs.9b10870

data_4133805
_publ_section_title
;
 Electrochemical Synthesis of Hindered Primary and Secondary Amines via
 Proton-Coupled Electron Transfer
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_paper_doi               10.1021/jacs.9b10870
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C16 H19 N5'
_chemical_formula_sum            'C16 H19 N5'
_chemical_formula_weight         281.36
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2019-07-31
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                90
_cell_angle_beta                 113.2490(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.4025(7)
_cell_length_b                   8.9323(5)
_cell_length_c                   14.1616(8)
_cell_measurement_reflns_used    9090
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      70.114
_cell_measurement_theta_min      4.024
_cell_volume                     1441.47(14)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_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, 2015)'
_diffrn_ambient_temperature      100.15
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_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  0.0219
_diffrn_reflns_av_unetI/netI     0.0129
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            20859
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         69.993
_diffrn_reflns_theta_min         6.009
_diffrn_source                   'sealed-tube microsource X-ray generator'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.643
_exptl_absorpt_correction_T_max  0.7533
_exptl_absorpt_correction_T_min  0.6893
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2014/5 (Bruker,2014/5) was used for absorption correction. wR2(int) was 0.0610 before and 0.0337 after correction. The Ratio of minimum to maximum transmission is 0.9150. The \l/2 correction factor is 0.00150.'
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.296
_exptl_crystal_description       block
_exptl_crystal_F_000             600
_exptl_crystal_recrystallization_method '1:1 v/v CD3OD / CD2Cl2'
_exptl_crystal_size_max          0.34
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.22
_refine_diff_density_max         0.311
_refine_diff_density_min         -0.191
_refine_diff_density_rms         0.035
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.052
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     197
_refine_ls_number_reflns         2724
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.052
_refine_ls_R_factor_all          0.0331
_refine_ls_R_factor_gt           0.0330
_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^)+(0.0392P)^2^+0.5679P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0833
_refine_ls_wR_factor_ref         0.0834
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2712
_reflns_number_total             2724
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b10870_si_002.cif
_cod_data_source_block           mdo033
_cod_database_code               4133805
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.872
_shelx_estimated_absorpt_t_min   0.811
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C13(H13A,H13B), C14(H14A,H14B), C15(H15A,H15B)
2.b Aromatic/amide H refined with riding coordinates:
 C5(H5), C10(H10), C17(H17), C18(H18), C19(H19), C20(H20), C21(H21), N11(H11)
2.c Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C)
;
_shelx_res_checksum              82975
_shelx_hkl_checksum              46819
_olex2_exptl_crystal_mounting_method
'mounted on a cryop loop with Paratone N oil'
_olex2_submission_special_instructions 'No special instructions were received'