Catalytic Asymmetric Hydroalkylation of α,β-Unsaturated Amides Enabled by Regio-Reversed and Enantiodifferentiating syn-Hydronickellation
Zhou, Fang; Zhu, Shaolin; ACS Catalysis 11 (2021) 8766–8773; doi:10.1021/acscatal.1c02299

data_4518946
_publ_section_title
;
 Catalytic Asymmetric Hydroalkylation of \a,\b-Unsaturated Amides Enabled
 by Regio-Reversed and Enantiodifferentiating syn-Hydronickellation
;
_journal_issue                   14
_journal_name_full               'ACS Catalysis'
_journal_page_first              8766
_journal_page_last               8773
_journal_paper_doi               10.1021/acscatal.1c02299
_journal_volume                  11
_journal_year                    2021
_chemical_absolute_configuration unk
_chemical_formula_moiety         'C20 H25 N O'
_chemical_formula_sum            'C20 H25 N O'
_chemical_formula_weight         295.41
_space_group_crystal_system      trigonal
_space_group_IT_number           145
_space_group_name_Hall           'P 32'
_space_group_name_H-M_alt        'P 32'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2021-01-05
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6226)
;
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                120.00
_cell_formula_units_Z            3
_cell_length_a                   10.1942(9)
_cell_length_b                   10.1942(9)
_cell_length_c                   14.1934(17)
_cell_measurement_reflns_used    3256
_cell_measurement_temperature    193
_cell_measurement_theta_max      27.40
_cell_measurement_theta_min      2.717
_cell_volume                     1277.4(2)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_diffrn_ambient_temperature      193
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0765
_diffrn_reflns_av_unetI/netI     0.0756
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            11907
_diffrn_reflns_theta_full        27.47
_diffrn_reflns_theta_max         27.47
_diffrn_reflns_theta_min         2.31
_diffrn_source                   'fine-focus sealed tube'
_diffrn_source_current           40.0
_diffrn_source_power             2.0
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.070
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.6205
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1803 before and 0.1114 after correction.
The Ratio of minimum to maximum transmission is 0.8322.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            white
_exptl_crystal_colour_primary    white
_exptl_crystal_density_diffrn    1.152
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             480
_exptl_crystal_size_max          0.17
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.11
_refine_diff_density_max         0.155
_refine_diff_density_min         -0.161
_refine_diff_density_rms         0.036
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   1.8(17)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.032
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     201
_refine_ls_number_reflns         3648
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.032
_refine_ls_R_factor_all          0.0712
_refine_ls_R_factor_gt           0.0517
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0530P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1150
_refine_ls_wR_factor_ref         0.1263
_reflns_number_gt                2847
_reflns_number_total             3648
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            cs1c02299_si_003.cif
_cod_data_source_block           wpl2021040103_0m_a
_cod_database_code               4518946
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C8(H8), C10(H10)
2.b Secondary CH2 refined with riding coordinates:
 C12(H12A,H12B), C13(H13A,H13B), C14(H14A,H14B)
2.c Aromatic/amide H refined with riding coordinates:
 N002(H002), C6(H6), C16(H16), C20(H20), C5(H5), C2(H2), C17(H17), C4(H4),
 C3(H3), C18(H18), C19(H19)
2.d Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C), C11(H11A,H11B,H11C)
;
_olex2_submission_special_instructions 'No special instructions were received'