Nickel(ii)-catalyzed enantioselective α-alkylation of β-ketoamides with phenyliodonium ylide via a radical process.
Guo, Jing; Liu, Xiaohua; He, Changqiang; Tan, Fei; Dong, Shunxi; Feng, Xiaoming; Chemical communications (Cambridge, England) 54 (2018) 12254–12257; doi:10.1039/c8cc07140c

data_7122421
_publ_section_title
;
 Nickel(ii)-catalyzed enantioselective \a-alkylation of \b-ketoamides with
 phenyliodonium ylide via a radical process.
;
_journal_issue                   86
_journal_name_full
'Chemical communications (Cambridge, England)'
_journal_page_first              12254
_journal_page_last               12257
_journal_paper_doi               10.1039/c8cc07140c
_journal_volume                  54
_journal_year                    2018
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C43 H68 N4 Ni O6, 2(Cl O4)'
_chemical_formula_sum            'C43 H68 Cl2 N4 Ni O14'
_chemical_formula_weight         994.62
_space_group_crystal_system      tetragonal
_space_group_IT_number           96
_space_group_name_Hall           'P 4nw 2abw'
_space_group_name_H-M_alt        'P 43 21 2'
_symmetry_space_group_name_Hall  'P 4nw 2abw'
_symmetry_space_group_name_H-M   'P 43 21 2'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-01-15
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2018-03-22 deposited with the CCDC.
2018-10-05 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.9026(2)
_cell_length_b                   12.9026(2)
_cell_length_c                   29.8458(7)
_cell_measurement_reflns_used    6782
_cell_measurement_temperature    293.2(2)
_cell_measurement_theta_max      60.2230
_cell_measurement_theta_min      4.5290
_cell_volume                     4968.64(16)
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      293.2(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 15.9595
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w     20.00 104.00   1.00   12.00    --   36.54  57.00 150.00   84
  2  \w     20.00 104.00   1.00   12.00    --   36.54  57.00-150.00   84
  3  \w     20.00 104.00   1.00   12.00    --   36.54  57.00-120.00   84
  4  \w     23.00  90.00   1.00   12.00    --   36.54-125.00-180.00   67
  5  \w     18.00 106.00   1.00   12.00    --   36.54  38.00-150.00   88
  6  \w     23.00  78.00   1.00   12.00    --   36.54  57.00 -60.00   55
  7  \w    -32.00  92.00   1.00   12.00    --   36.54   0.00  30.00  124
  8  \w     28.00  54.00   1.00   12.00    --   36.54-125.00-120.00   26
  9  \w    120.00 176.00   1.00   42.50    --  108.00  77.00 150.00   56
 10  \w     90.00 116.00   1.00   42.50    --  108.00  61.00-180.00   26
 11  \w     82.00 107.00   1.00   42.50    --  108.00  77.00 150.00   25
 12  \w     92.00 130.00   1.00   42.50    --  108.00  45.00-150.00   38
 13  \w     90.00 121.00   1.00   42.50    --  108.00  61.00-150.00   31
 14  \w    125.00 174.00   1.00   42.50    --  108.00  61.00-150.00   49
 15  \w    139.00 173.00   1.00   42.50    --  108.00  77.00-180.00   34
 16  \w     38.00  63.00   1.00   42.50    --  108.00 -30.00  30.00   25
 17  \w     87.00 113.00   1.00   42.50    --  108.00  30.00-150.00   26
 18  \w     43.00 105.00   1.00   42.50    --  108.00 -94.00  90.00   62
 19  \w     87.00 113.00   1.00   42.50    --  108.00  30.00-120.00   26
 20  \w     94.00 121.00   1.00   42.50    --  108.00  45.00-180.00   27
 21  \w     59.00  87.00   1.00   42.50    --  108.00 -30.00-150.00   28
 22  \w     51.00  82.00   1.00   42.50    --  108.00 -94.00-180.00   31
 23  \w     43.00  98.00   1.00   42.50    --  108.00 -45.00  60.00   55
 24  \w     90.00 116.00   1.00   42.50    --  108.00  61.00 150.00   26
 25  \w     81.00 107.00   1.00   42.50    --  108.00  77.00-180.00   26
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'New Gemini, Dual, Cu at zero, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0486751000
_diffrn_orient_matrix_UB_12      0.0889068000
_diffrn_orient_matrix_UB_13      0.0272302000
_diffrn_orient_matrix_UB_21      0.0956069000
_diffrn_orient_matrix_UB_22      -0.0680704000
_diffrn_orient_matrix_UB_23      0.0096404000
_diffrn_orient_matrix_UB_31      0.0525209000
_diffrn_orient_matrix_UB_32      0.0413050000
_diffrn_orient_matrix_UB_33      -0.0427777000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0296
_diffrn_reflns_av_unetI/netI     0.0146
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       35
_diffrn_reflns_limit_l_min       -35
_diffrn_reflns_number            26123
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        67.072
_diffrn_reflns_theta_max         67.072
_diffrn_reflns_theta_min         4.530
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.101
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.55987
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear green'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.330
_exptl_crystal_description       block
_exptl_crystal_F_000             2112
_exptl_crystal_size_max          0.32
_exptl_crystal_size_mid          0.28
_exptl_crystal_size_min          0.24
_refine_diff_density_max         0.442
_refine_diff_density_min         -0.234
_refine_diff_density_rms         0.058
_refine_ls_abs_structure_details
;
 Flack x determined using 1067 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.010(11)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.019
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     280
_refine_ls_number_reflns         4449
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.019
_refine_ls_R_factor_all          0.0919
_refine_ls_R_factor_gt           0.0745
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1610P)^2^+1.1010P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2282
_refine_ls_wR_factor_ref         0.2564
_reflns_Friedel_coverage         0.697
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     1.000
_reflns_number_gt                3240
_reflns_number_total             4449
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8cc07140c2.cif
_cod_data_source_block           fxm-gj-1
_cod_depositor_comments
'Adding full bibliography for 7122420--7122421.cif.'
_cod_original_cell_volume        4968.6(2)
_cod_database_code               7122421
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.633
_shelx_estimated_absorpt_t_min   0.553
_reflns_odcompleteness_completeness 99.85
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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. Rigid bond restraints
 C4
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
3. Uiso/Uaniso restraints and constraints
C10: within 2A with sigma of 0.02 and sigma for terminal atoms of 0.04
4. Others
 Fixed Sof: H00V(0.5) H00W(0.5)
5.a Ternary CH refined with riding coordinates:
 C008(H008)
5.b Secondary CH2 refined with riding coordinates:
 C00C(H00B,H00C), C00E(H00D,H00E), C00F(H00F,H00G), C00I(H00H,H00I), C00J(H00J,
 H00K), C00K(H00L,H00M), C00L(H00N,H00O), C00M(H00P,H00Q), C00N(H00R,H00S),
 C1AA(H1AA,H1AB), C007(H00T,H00U), C009(H00V,H00W)
5.c Aromatic/amide H refined with riding coordinates:
 N00A(H00A), C3(H3), C4(H4), C5(H5)
5.d Fitted hexagon refined as free rotating group:
 C1(C2,C3,C4,C5,C6)
5.e Idealised Me refined as rotating group:
 C0AA(H0AA,H0AB,H0AC), C10(H10A,H10B,H10C)
;
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.771
_oxdiff_exptl_absorpt_empirical_full_min 0.699