Synthesis of Enantioenriched Allylic Silanes via Nickel-Catalyzed Reductive Cross-Coupling.
Hofstra, Julie L.; Cherney, Alan H.; Ordner, Ciara M.; Reisman, Sarah E.; Journal of the American Chemical Society  (2017) –; doi:10.1021/jacs.7b11707

data_4126956
_publ_section_title
;
 Synthesis of Enantioenriched Allylic Silanes via Nickel-Catalyzed
 Reductive Cross-Coupling.
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_paper_doi               10.1021/jacs.7b11707
_journal_year                    2017
_chemical_absolute_configuration ad
_chemical_formula_moiety
'C69 H60 Cl6 N6 Ni3 O6, 1.27(C H2 Cl2), 0.73(C2 H3 N)'
_chemical_formula_sum            'C71.73 H64.73 Cl8.54 N6.73 Ni3 O6'
_chemical_formula_weight         1595.88
_chemical_name_common            JLH-5-218
_chemical_name_systematic        JLH-5-218
_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
_atom_sites_solution_secondary   difmap
_audit_creation_date             2017-02-07
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                90
_cell_angle_beta                 116.546(4)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   14.8277(18)
_cell_length_b                   15.771(2)
_cell_length_c                   16.569(2)
_cell_measurement_reflns_used    9266
_cell_measurement_temperature    100
_cell_measurement_theta_max      36.26
_cell_measurement_theta_min      2.48
_cell_volume                     3466.1(7)
_computing_cell_refinement       'SAINT v8.34A (Bruker-AXS, 2007)'
_computing_data_collection       'APEX2 v2014.11-0 (Bruker-AXS, 2014)'
_computing_data_reduction        'SAINT v8.34A (Bruker-AXS, 2007)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_structure_solution    'SHELXS-2013/1 (She ldrick, 2013)'
_diffrn_ambient_temperature      100
_diffrn_detector                 'CMOS Area Detector'
_diffrn_detector_area_resol_mean 10.24
_diffrn_detector_type            'Bruker PHOTON 100 CMOS'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device       '\k-geometry diffractometer'
_diffrn_measurement_device_type  'Bruker D8 VENTURE Kappa Duo PHOTON 100 CMOS'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  'multilayer mirrors'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0487
_diffrn_reflns_av_unetI/netI     0.0485
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            214882
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         36.402
_diffrn_reflns_theta_min         2.476
_diffrn_source                   'I\mS HB micro-focus sealed tube'
_diffrn_source_current           1
_diffrn_source_power             0.05
_diffrn_source_type              'Incoatech I\mS HB'
_diffrn_source_voltage           50
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.194
_exptl_absorpt_correction_T_max  0.7471
_exptl_absorpt_correction_T_min  0.6863
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SADABS-2014/5 (Sheldrick, 2014)'
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.529
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       Block
_exptl_crystal_F_000             1639
_exptl_crystal_size_max          0.30
_exptl_crystal_size_mid          0.30
_exptl_crystal_size_min          0.15
_refine_diff_density_max         1.137
_refine_diff_density_min         -1.072
_refine_diff_density_rms         0.090
_refine_ls_abs_structure_details
;
 Flack x determined using 12016 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.0162(19)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.022
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     894
_refine_ls_number_reflns         33574
_refine_ls_number_restraints     8
_refine_ls_restrained_S_all      1.022
_refine_ls_R_factor_all          0.0541
_refine_ls_R_factor_gt           0.0388
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0417P)^2^+1.4314P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0842
_refine_ls_wR_factor_ref         0.0891
_reflns_Friedel_coverage         0.941
_reflns_Friedel_fraction_full    0.997
_reflns_Friedel_fraction_max     0.991
_reflns_number_gt                28667
_reflns_number_total             33574
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b11707_si_003.cif
_cod_data_source_block           p16408
_cod_original_cell_volume        3466.1(8)
_cod_database_code               4126956
_shelx_estimated_absorpt_t_max   0.841
_shelx_estimated_absorpt_t_min   0.716
_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
2. Restrained distances
 C1S-Cl1S \\sim C1S-Cl2S \\sim C2T-Cl3T \\sim C2T-Cl4T
 with sigma of 0.02
 Cl1S-Cl2S \\sim Cl3T-Cl4T
 with sigma of 0.02
3. Others
 Sof(C2T)=Sof(H2TA)=Sof(H2TB)=Sof(Cl3T)=Sof(Cl4T)=1-FVAR(1)
 Sof(N1S)=Sof(C11S)=Sof(C12S)=Sof(H12A)=Sof(H12B)=Sof(H12C)=FVAR(1)
4.a Ternary CH refined with riding coordinates:
 C1(H1), C9(H9), C13(H13), C21(H21), C31(H31), C39(H39), C43(H43), C51(H51),
 C61(H61), C69(H69), C73(H73), C81(H81)
4.b Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C22(H22A,H22B), C23(H23A,H23B), C14(H14A,H14B), C38(H38A,H38B),
 C52(H52A,H52B), C53(H53A,H53B), C44(H44A,H44B), C68(H68A,H68B), C82(H82A,H82B),
  C83(H83A,H83B), C74(H74A,H74B), C1S(H1SA,H1SB), C2T(H2TA,H2TB)
4.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C6(H6), C16(H16), C17(H17), C18(H18), C19(H19),
 C33(H33), C34(H34), C35(H35), C36(H36), C46(H46), C47(H47), C48(H48), C49(H49),
  C63(H63), C64(H64), C65(H65), C66(H66), C76(H76), C77(H77), C78(H78), C79(H79)
4.d Idealised Me refined as rotating group:
 C12S(H12A,H12B,H12C)
;
_shelx_res_checksum              53561
_shelx_hkl_checksum              65078
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'