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_4122998
_publ_section_title
;
 Nickel-Catalyzed Negishi Arylations of Propargylic Bromides:
 A&#x00A0;Mechanistic Investigation.
;
_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 ad
_chemical_formula_moiety         'C23 H28 N3 Ni O2'
_chemical_formula_sum            'C23 H28 N3 Ni O2'
_chemical_formula_weight         437.19
_chemical_name_systematic
;
 ? 
;
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_symmetry_cell_setting           monoclinic
_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             2013-03-19
_audit_creation_method
;
  Olex2 1.2
  (compiled Dec  5 2012 16:17:34, GUI svn.r4385)
;
_cell_angle_alpha                90.00
_cell_angle_beta                 99.75(3)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   10.450(2)
_cell_length_b                   11.491(2)
_cell_length_c                   18.143(4)
_cell_measurement_temperature    100
_cell_volume                     2147.2(8)
_computing_molecular_graphics
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_publication_material
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_structure_refinement
;
XL, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_computing_structure_solution
;
XS, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_diffrn_ambient_temperature      100.15
_diffrn_measured_fraction_theta_full 0.958
_diffrn_measured_fraction_theta_max 0.880
_diffrn_measurement_device_type  SSRL
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_monochromator  Si
_diffrn_radiation_type           synchrotron
_diffrn_radiation_wavelength     0.72930
_diffrn_reflns_av_R_equivalents  0.0423
_diffrn_reflns_av_unetI/netI     0.0641
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            18095
_diffrn_reflns_theta_full        26.50
_diffrn_reflns_theta_max         31.38
_diffrn_reflns_theta_min         1.17
_diffrn_source                   synchrotron
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.927
_exptl_absorpt_correction_type   empirical
_exptl_crystal_colour            brown
_exptl_crystal_density_diffrn    1.352
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             924
_exptl_crystal_size_max          0.11
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.844
_refine_diff_density_min         -0.487
_refine_diff_density_rms         0.067
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.048(9)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.007
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     531
_refine_ls_number_reflns         9894
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.007
_refine_ls_R_factor_all          0.0446
_refine_ls_R_factor_gt           0.0401
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0514P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1013
_refine_ls_wR_factor_ref         0.1031
_reflns_number_gt                8839
_reflns_number_total             9894
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja508718m_si_001.cif
_cod_data_source_block           (i-Pr-Pybox)NiPh
_cod_original_cell_volume        2147.2(7)
_cod_database_code               4122998
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  H15 of C15, H11 of C11, H29 of C29, H20 of C20, H1 of C1, H38 of C38, {H10A,
  H10B} of C10, H7 of C7, {H25A,H25B} of C25, {H33A,H33B} of C33, H28 of C28,
  H5 of C5, H46 of C46, H34 of C34, H24 of C24, H19 of C19, {H2A,H2B} of C2, H6
  of C6, H30 of C30, H44 of C44, H12 of C12, H23 of C23, H43 of C43, H45 of C45,
   H22 of C22, H21 of C21, H35 of C35, H42 of C42
 At 1.5 times of:
  {H14A,H14B,H14C} of C14, {H39A,H39B,H39C} of C39, {H16A,H16B,H16C} of C16,
  {H13A,H13B,H13C} of C13, {H40A,H40B,H40C} of C40, {H17A,H17B,H17C} of C17,
  {H36A,H36B,H36C} of C36, {H37A,H37B,H37C} of C37
2.a Ternary CH refined with riding coordinates:
 C34(H34), C24(H24), C11(H11), C1(H1), C38(H38), C15(H15), C35(H35), C12(H12)
2.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C10(H10A,H10B), C25(H25A,H25B), C33(H33A,H33B)
2.c Aromatic/amide H refined with riding coordinates:
 C30(H30), C28(H28), C5(H5), C46(H46), C19(H19), C6(H6), C20(H20), C29(H29),
 C7(H7), C22(H22), C42(H42), C23(H23), C43(H43), C21(H21), C45(H45), C44(H44)
2.d Idealised Me refined as rotating group:
 C39(H39A,H39B,H39C), C14(H14A,H14B,H14C), C36(H36A,H36B,H36C), C40(H40A,H40B,
 H40C), C17(H17A,H17B,H17C), C16(H16A,H16B,H16C), C37(H37A,H37B,H37C), C13(H13A,
 H13B,H13C)
;