Enantioselective Nickel-Catalyzed Mizoroki‒Heck Cyclizations To Generate Quaternary Stereocenters
Desrosiers, Jean-Nicolas; Wen, Jialin; Tcyrulnikov, Sergei; Biswas, Soumik; Qu, Bo; Hie, Liana; Kurouski, Dmitry; Wu, Ling; Grinberg, Nelu; Haddad, Nizar; Busacca, Carl A.; Yee, Nathan K.; Song, Jinhua J.; Garg, Neil K.; Zhang, Xumu; Kozlowski, Marisa C.; Senanayake, Chris H.; Organic Letters  (2017) –; doi:10.1021/acs.orglett.7b01054

data_1546293
_publ_section_title
;
 Enantioselective Nickel-Catalyzed Mizoroki--Heck Cyclizations To Generate
 Quaternary Stereocenters
;
_journal_name_full               'Organic Letters'
_journal_paper_doi               10.1021/acs.orglett.7b01054
_journal_year                    2017
_chemical_formula_moiety         'C18 H28 Cl2 N2 Ni P2, C2 H6 O'
_chemical_formula_sum            'C20 H34 Cl2 N2 Ni O P2'
_chemical_formula_weight         510.04
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2017-02-14
_audit_creation_method
;
Olex2 1.2
(compiled 2016.11.30 svn.r3356 for OlexSys, GUI svn.r5269)
;
_cell_angle_alpha                90
_cell_angle_beta                 101.286(3)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   8.1504(4)
_cell_length_b                   14.5588(6)
_cell_length_c                   10.2533(5)
_cell_measurement_reflns_used    4335
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      66.466
_cell_measurement_theta_min      4.397
_cell_volume                     1193.13(10)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_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    'XS (Sheldrick, 2008)'
_diffrn_ambient_temperature      100.0
_diffrn_measured_fraction_theta_full 0.871
_diffrn_measured_fraction_theta_max 0.871
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0184
_diffrn_reflns_av_unetI/netI     0.0349
_diffrn_reflns_Laue_measured_fraction_full 0.871
_diffrn_reflns_Laue_measured_fraction_max 0.871
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            5587
_diffrn_reflns_point_group_measured_fraction_full 0.770
_diffrn_reflns_point_group_measured_fraction_max 0.769
_diffrn_reflns_theta_full        66.498
_diffrn_reflns_theta_max         66.498
_diffrn_reflns_theta_min         4.397
_exptl_absorpt_coefficient_mu    4.605
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.8649
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0516 before and 0.0415 after correction.
The Ratio of minimum to maximum transmission is 0.8649.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            orange
_exptl_crystal_density_diffrn    1.420
_exptl_crystal_F_000             536
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.259
_refine_diff_density_min         -0.194
_refine_diff_density_rms         0.042
_refine_ls_abs_structure_details
;
 Flack x determined using 1272 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.059(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.023
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     263
_refine_ls_number_reflns         3228
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.023
_refine_ls_R_factor_all          0.0207
_refine_ls_R_factor_gt           0.0202
_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^)+(0.0232P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0484
_refine_ls_wR_factor_ref         0.0486
_reflns_Friedel_coverage         0.694
_reflns_Friedel_fraction_full    0.659
_reflns_Friedel_fraction_max     0.659
_reflns_number_gt                3174
_reflns_number_total             3228
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ol7b01054_si_002.cif
_cod_data_source_block           scan_0m
_cod_database_code               1546293
_shelx_estimated_absorpt_t_max   0.874
_shelx_estimated_absorpt_t_min   0.545
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
2.a Secondary CH2 refined with riding coordinates:
 C20(H20A,H20B)
2.b Aromatic/amide H refined with riding coordinates:
 C14(H14), C15(H15), C16(H16), C17(H17)
2.c Idealised Me refined as rotating group:
 C2(H2A,H2B,H2C), C3(H3A,H3B,H3C), C4(H4A,H4B,H4C), C5(H5A,H5B,H5C), C9(H9A,
 H9B,H9C), C10(H10A,H10B,H10C), C11(H11A,H11B,H11C), C12(H12A,H12B,H12C),
 C19(H19A,H19B,H19C)
2.d Idealised tetrahedral OH refined as rotating group:
 O1(H1)
;
_shelx_res_checksum              75904
_shelx_hkl_checksum              32453
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'