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_4126957
_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         'C24 H33 B1 O2 Si'
_chemical_formula_sum            'C24 H33 B O2 Si'
_chemical_formula_weight         392.40
_chemical_name_common            JLH-4-295
_chemical_name_systematic        JLH-4-295
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2016-10-10
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   6.4080(3)
_cell_length_b                   12.5679(5)
_cell_length_c                   30.4781(13)
_cell_measurement_reflns_used    7590
_cell_measurement_temperature    270
_cell_measurement_theta_max      20.96
_cell_measurement_theta_min      2.58
_cell_volume                     2454.56(18)
_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      270
_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 0.998
_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  0.0848
_diffrn_reflns_av_unetI/netI     0.0898
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       39
_diffrn_reflns_limit_l_min       -39
_diffrn_reflns_number            31898
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.515
_diffrn_reflns_theta_min         2.578
_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    0.111
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.6970
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SADABS-2014/5 (Sheldrick, 2014)'
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.062
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             848
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.141
_refine_diff_density_min         -0.193
_refine_diff_density_rms         0.037
_refine_ls_abs_structure_details
;
 Flack x determined using 928 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.02(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.037
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     421
_refine_ls_number_reflns         5646
_refine_ls_number_restraints     1045
_refine_ls_restrained_S_all      0.980
_refine_ls_R_factor_all          0.1483
_refine_ls_R_factor_gt           0.0626
_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^)+(0.0529P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1005
_refine_ls_wR_factor_ref         0.1207
_reflns_Friedel_coverage         0.739
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.998
_reflns_number_gt                3088
_reflns_number_total             5646
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b11707_si_004.cif
_cod_data_source_block           mkt
_cod_database_code               4126957
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Rigid bond restraints
 C4, B1, O1, C0AA, C1AA, C2AA, C3AA, C4AA, C5AA, O2, B1A, O1A, C4A, C5A, C6A,
 C7A, C8A, C9A, O2A, B1B, O1B, C4B, C5B, C6B, C7B, C8B, C9B, O2B
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
3. Uiso/Uaniso restraints and constraints
C4 \\sim B1 \\sim O1 \\sim C0AA \\sim C1AA \\sim C2AA \\sim C3AA \\sim C4AA
\\sim C5AA \\sim O2 \\sim B1A \\sim O1A \\sim C4A \\sim C5A \\sim C6A \\sim C7A
\\sim C8A \\sim C9A \\sim O2A \\sim B1B \\sim O1B \\sim C4B \\sim C5B \\sim C6B
\\sim C7B \\sim C8B \\sim C9B \\sim O2B: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08
4. Same fragment restrains
{C4, B1, O1, C0AA, C2AA, C1AA, C3AA, C5AA, C4AA, O2} sigma for 1-2: 0.02, 1-3:
0.04
{C4, B1, O2, C3AA, C4AA, C5AA, C0AA, C1AA, C2AA, O1} sigma for 1-2: 0.02, 1-3:
0.04
{C4, B1A, O1A, C4A, C5A, C6A, C7A, C8A, C9A, O2A} sigma for 1-2: 0.02, 1-3: 0.04
{C4, B1B, O1B, C4B, C5B, C6B, C7B, C8B, C9B, O2B} sigma for 1-2: 0.02, 1-3: 0.04
as
{C4, B1, O1, C0AA, C1AA, C2AA, C3AA, C4AA, C5AA, O2}
5. Others
 1*[Sof(B1)+Sof(O1)+Sof(C0AA)+Sof(C1AA)+Sof(H1AA)+Sof(H1AB)+Sof(H1AC)+
 Sof(C2AA)+Sof(H2AA)+Sof(H2AB)+Sof(H2AC)+Sof(C3AA)+Sof(C4AA)+Sof(H4AA)+
 Sof(H4AB)+Sof(H4AC)+Sof(C5AA)+Sof(H5AA)+Sof(H5AB)+Sof(H5AC)+Sof(O2)]+1*
 [Sof(B1A)+Sof(O1A)+Sof(C4A)+Sof(C5A)+Sof(H5AD)+Sof(H5AE)+Sof(H5AF)+Sof(C6A)+
 Sof(H6AA)+Sof(H6AB)+Sof(H6AC)+Sof(C7A)+Sof(C8A)+Sof(H8AA)+Sof(H8AB)+Sof(H8AC)+
 Sof(C9A)+Sof(H9AA)+Sof(H9AB)+Sof(H9AC)+Sof(O2A)]+1*[Sof(B1B)+Sof(O1B)+Sof(C4B)+
 Sof(C5B)+Sof(H5BA)+Sof(H5BB)+Sof(H5BC)+Sof(C6B)+Sof(H6BA)+Sof(H6BB)+Sof(H6BC)+
 Sof(C7B)+Sof(C8B)+Sof(H8BA)+Sof(H8BB)+Sof(H8BC)+Sof(C9B)+Sof(H9BA)+Sof(H9BB)+
 Sof(H9BC)+Sof(O2B)]=1 with esd of 0
 Sof(B1)=Sof(O1)=Sof(C0AA)=Sof(C1AA)=Sof(H1AA)=Sof(H1AB)=Sof(H1AC)=Sof(C2AA)=
 Sof(H2AA)=Sof(H2AB)=Sof(H2AC)=Sof(C3AA)=Sof(C4AA)=Sof(H4AA)=Sof(H4AB)=
 Sof(H4AC)=Sof(C5AA)=Sof(H5AA)=Sof(H5AB)=Sof(H5AC)=Sof(O2)=FVAR(1)
 Sof(B1A)=Sof(O1A)=Sof(C4A)=Sof(C5A)=Sof(H5AD)=Sof(H5AE)=Sof(H5AF)=Sof(C6A)=
 Sof(H6AA)=Sof(H6AB)=Sof(H6AC)=Sof(C7A)=Sof(C8A)=Sof(H8AA)=Sof(H8AB)=Sof(H8AC)=
 Sof(C9A)=Sof(H9AA)=Sof(H9AB)=Sof(H9AC)=Sof(O2A)=FVAR(2)
 Sof(B1B)=Sof(O1B)=Sof(C4B)=Sof(C5B)=Sof(H5BA)=Sof(H5BB)=Sof(H5BC)=Sof(C6B)=
 Sof(H6BA)=Sof(H6BB)=Sof(H6BC)=Sof(C7B)=Sof(C8B)=Sof(H8BA)=Sof(H8BB)=Sof(H8BC)=
 Sof(C9B)=Sof(H9BA)=Sof(H9BB)=Sof(H9BC)=Sof(O2B)=FVAR(3)
6.a Ternary CH refined with riding coordinates:
 C12(H12)
6.b Me refined with riding coordinates:
 C1AA(H1AA,H1AB,H1AC), C2AA(H2AA,H2AB,H2AC), C4AA(H4AA,H4AB,H4AC), C5AA(H5AA,
 H5AB,H5AC), C5A(H5AD,H5AE,H5AF), C6A(H6AA,H6AB,H6AC), C8A(H8AA,H8AB,H8AC),
 C9A(H9AA,H9AB,H9AC), C5B(H5BA,H5BB,H5BC), C6B(H6BA,H6BB,H6BC), C8B(H8BA,H8BB,
 H8BC), C9B(H9BA,H9BB,H9BC)
6.c Aromatic/amide H refined with riding coordinates:
 C10(H10), C8(H8), C11(H11), C14(H14), C18(H18), C9(H9), C6(H6), C5(H5),
 C15(H15), C17(H17), C16(H16)
6.d Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C3(H3A,H3B,H3C), C2(H2A,H2B,H2C)
;
_shelx_res_checksum              29120
_shelx_hkl_checksum              85990
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'