Nickel-Catalyzed Negishi Arylations of Propargylic Bromides: A Mechanistic Investigation.
Schley, Nathan D.; Fu, Gregory C.; Journal of the American Chemical Society  (2014) 141117163347008–; doi:10.1021/ja508718m

data_4122997
_publ_section_title
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 Nickel-Catalyzed Negishi Arylations of Propargylic Bromides:
 A&#x00A0;Mechanistic Investigation.
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_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              141117163347008
_journal_paper_doi               10.1021/ja508718m
_journal_year                    2014
_chemical_absolute_configuration rmad
_chemical_formula_moiety         'C23 H28 N3 Ni O2, C32 H12 B F24, 2(C6 H6)'
_chemical_formula_sum            'C67 H52 B F24 N3 Ni O2'
_chemical_formula_weight         1456.63
_chemical_name_systematic
;
 ?
;
_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
_audit_creation_date             2014-02-11
_audit_creation_method
;
Olex2 1.2
(compiled 2013.12.10 svn.r2850 for OlexSys, GUI svn.r4736)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.0108(13)
_cell_length_b                   13.0547(13)
_cell_length_c                   37.484(4)
_cell_measurement_reflns_used    9038
_cell_measurement_temperature    100
_cell_measurement_theta_max      25.23
_cell_measurement_theta_min      2.28
_cell_volume                     6366.7(11)
_computing_cell_refinement       'SAINT v6.45A (Bruker, 2003)'
_computing_data_reduction        'SAINT v8.27A (Bruker, 2012)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'XS (Sheldrick, 2008)'
_diffrn_ambient_temperature      100
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.994
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0552
_diffrn_reflns_av_unetI/netI     0.0443
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       48
_diffrn_reflns_limit_l_min       -48
_diffrn_reflns_number            79002
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         27.673
_diffrn_reflns_theta_min         1.652
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.423
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.9023
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.0586 before and 0.0536 after correction.
The Ratio of minimum to maximum transmission is 0.9023.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.520
_exptl_crystal_description       prism
_exptl_crystal_F_000             2960
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.395
_refine_diff_density_min         -0.283
_refine_diff_density_rms         0.053
_refine_ls_abs_structure_details
;
 Flack x determined using 4721 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   -0.017(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.026
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     944
_refine_ls_number_reflns         14748
_refine_ls_number_restraints     85
_refine_ls_restrained_S_all      1.032
_refine_ls_R_factor_all          0.0568
_refine_ls_R_factor_gt           0.0400
_refine_ls_shift/su_max          0.018
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
;
 w=1/[\s^2^(Fo^2^)+(0.0327P)^2^+2.4748P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0777
_refine_ls_wR_factor_ref         0.0848
_reflns_Friedel_coverage         0.815
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.991
_reflns_number_gt                12078
_reflns_number_total             14748
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja508718m_si_001.cif
_cod_data_source_block           '[(i-Pr-Pybox)NiPh]BArF4'
_cod_original_cell_volume        6366.8(11)
_cod_database_code               4122997
_shelxl_version_number           2013-2
_shelx_estimated_absorpt_t_max   0.939
_shelx_estimated_absorpt_t_min   0.883
_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. Uiso/Uaniso restraints and constraints
F11A \\sim F10B \\sim F10A \\sim F12B \\sim F12A \\sim F11B \\sim F12 \\sim F10
\\sim F11: within 1.7A with sigma of 0.002 and sigma for terminal atoms of 0.004
3. Others
 1*[Sof(F10)+Sof(F11)+Sof(F12)]+1*[Sof(F10A)+Sof(F11A)+Sof(F12A)]+1*[Sof(F10B)+
 Sof(F11B)+Sof(F12B)]=1 with esd of 0.00001
 Sof(F10)=Sof(F11)=Sof(F12)=FVAR(1)
 Sof(F10A)=Sof(F11A)=Sof(F12A)=FVAR(2)
 Sof(F10B)=Sof(F11B)=Sof(F12B)=FVAR(3)
4.a Ternary CH refined with riding coordinates:
 C1(H1), C11(H11), C12(H12), C15(H15)
4.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C10(H10A,H10B)
4.c Aromatic/amide H refined with riding coordinates:
 C5(H5), C6(H6), C7(H7), C19(H19), C20(H20), C21(H21), C22(H22), C23(H23),
 C25(H25), C27(H27), C29(H29), C33(H33), C35(H35), C37(H37), C41(H41), C43(H43),
  C45(H45), C49(H49), C51(H51), C53(H53), C62(H62), C63(H63), C64(H64),
 C65(H65), C66(H66), C67(H67), C56(H56), C57(H57), C58(H58), C59(H59), C60(H60),
  C61(H61)
4.d Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C16(H16A,H16B,H16C), C17(H17A,H17B,
 H17C)
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