Ni-catalyzed enantioselective three-component reductive alkylacylation of alkenes: modular access to structurally complex α-amino ketones.
Xiao, Jichao; Jia, Tingting; Chen, Shuang; Pan, Mengxiao; Li, Xingwei; Chemical science 15 (2024) 15489–15495; doi:10.1039/d4sc04561k

data_1572493
_publ_section_title
;
 Ni-catalyzed enantioselective three-component reductive alkylacylation of
 alkenes: modular access to structurally complex &#x3b1;-amino ketones.
;
_journal_issue                   37
_journal_name_full               'Chemical science'
_journal_page_first              15489
_journal_page_last               15495
_journal_paper_doi               10.1039/d4sc04561k
_journal_volume                  15
_journal_year                    2024
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C21 H23 Br Cl N O2'
_chemical_formula_sum            'C21 H23 Br Cl N O2'
_chemical_formula_weight         436.76
_space_group_crystal_system      trigonal
_space_group_IT_number           144
_space_group_name_Hall           'P 31'
_space_group_name_H-M_alt        'P 31'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2024-03-29
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-05-21 deposited with the CCDC.	2024-09-04 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            6
_cell_length_a                   17.0757(3)
_cell_length_b                   17.0757(3)
_cell_length_c                   13.5351(3)
_cell_measurement_reflns_used    9841
_cell_measurement_temperature    200.00
_cell_measurement_theta_max      68.284
_cell_measurement_theta_min      2.989
_cell_volume                     3417.82(11)
_computing_cell_refinement       'SAINT V8.40A (Bruker, 2019)'
_computing_data_reduction        'SAINT V8.40A (Bruker, 2019)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/2 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      200.00
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.999
_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  0.0475
_diffrn_reflns_av_unetI/netI     0.0321
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            41263
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         68.322
_diffrn_reflns_theta_min         2.988
_diffrn_source_current           50.0
_diffrn_source_power             2.5
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    3.638
_exptl_absorpt_correction_T_max  0.7531
_exptl_absorpt_correction_T_min  0.5076
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1237 before and 0.0734 after correction.
The Ratio of minimum to maximum transmission is 0.6740.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'clear yellowish colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   yellowish
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.273
_exptl_crystal_description       block
_exptl_crystal_F_000             1344
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.417
_refine_diff_density_min         -0.545
_refine_diff_density_rms         0.074
_refine_ls_abs_structure_details
;
 Flack x determined using 3104 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.031(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.049
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     505
_refine_ls_number_reflns         8369
_refine_ls_number_restraints     84
_refine_ls_restrained_S_all      1.236
_refine_ls_R_factor_all          0.0731
_refine_ls_R_factor_gt           0.0662
_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^)+(0.1524P)^2^+0.3823P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1941
_refine_ls_wR_factor_ref         0.2039
_reflns_Friedel_coverage         0.998
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.997
_reflns_number_gt                7149
_reflns_number_total             8369
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc04561k2.cif
_cod_data_source_block           s_CCDC1
_cod_depositor_comments
'Adding full bibliography for 1572492--1572493.cif.'
_cod_original_cell_volume        3417.82(14)
_cod_database_code               1572493
_shelx_shelxl_version_number     2019/2
_shelx_estimated_absorpt_t_max   0.712
_shelx_estimated_absorpt_t_min   0.408
_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. Restrained distances
 Br03-C3 \\sim Br-C3A
 with sigma of 0.02
 C011-C01D \\sim C011-C1
 with sigma of 0.02
 C01D-C3 \\sim C1-C3A
 with sigma of 0.02
 Br03-C01D \\sim Br-C1
 with sigma of 0.04
 C011-C3 \\sim C011-C3A
 with sigma of 0.04
3. Rigid bond restraints
 Br03, C01D, C3, C3A, Br, C1
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
Br03 \\sim C01D \\sim C3 \\sim C3A \\sim Br \\sim C1: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
Uanis(Cl05) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
5. Others
 Sof(C3A)=Sof(H3AA)=Sof(H3AB)=Sof(Br)=Sof(C1)=Sof(H1A)=Sof(H1B)=1-FVAR(1)
 Sof(Br03)=Sof(C01D)=Sof(H01G)=Sof(H01H)=Sof(C3)=Sof(H3A)=Sof(H3B)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 C00E(H00E), C00O(H00O)
6.b Secondary CH2 refined with riding coordinates:
 C00Q(H00F,H00G), C00R(H00B,H00C), C013(H01M,H01N), C01D(H01G,H01H), C01E(H01U,
 H01V), C3(H3A,H3B), C3A(H3AA,H3AB), C1(H1A,H1B)
6.c Aromatic/amide H refined with riding coordinates:
 N00A(H00A), C00J(H00J), C00K(H00K), C00L(H00L), C00M(H00M), C00S(H00S),
 C00U(H00U), C00W(H00W), C00X(H00X), C00Y(H00Y), C00Z(H00Z), C010(H010),
 C012(H012), C017(H017), C018(H018), C01A(H01D), C01B(H01E), C01C(H01F),
 C01F(H01I)
6.d Idealised Me refined as rotating group:
 C015(H01O,H01P,H01Q), C016(H01R,H01S,H01T), C019(H01A,H01B,H01C), C01H(H01J,
 H01K,H01L)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              72559
_shelx_fab_checksum              11291
_olex2_submission_special_instructions 'No special instructions were received'