Selective Double Carbomagnesiation of Internal Alkynes Catalyzed by Iron-N-Heterocyclic Carbene Complexes: A Convenient Method to Highly Substituted 1,3-Dienyl Magnesium Reagents.
Liu, Yuesheng; Wang, Lijun; Deng, Liang; Journal of the American Chemical Society 138 (2016) 112–115; doi:10.1021/jacs.5b12522

data_4129983
_publ_section_title
;
 Selective Double Carbomagnesiation of Internal Alkynes Catalyzed by
 Iron-N-Heterocyclic Carbene Complexes: A Convenient Method to Highly
 Substituted 1,3-Dienyl Magnesium Reagents.
;
_journal_issue                   1
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              112
_journal_page_last               115
_journal_paper_doi               10.1021/jacs.5b12522
_journal_volume                  138
_journal_year                    2016
_chemical_absolute_configuration rmad
_chemical_formula_moiety         'C27 H25 N O4'
_chemical_formula_sum            'C27 H25 N O4'
_chemical_formula_weight         427.48
_space_group_crystal_system      orthorhombic
_space_group_IT_number           33
_space_group_name_Hall           'P 2c -2n'
_space_group_name_H-M_alt        'P n a 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2015-02-03
_audit_creation_method
;
Olex2 1.2
(compiled 2014.07.22 svn.r2960 for OlexSys, GUI svn.r4862)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   25.893(5)
_cell_length_b                   12.995(3)
_cell_length_c                   6.5547(14)
_cell_measurement_reflns_used    2669
_cell_measurement_temperature    130
_cell_measurement_theta_max      22.599
_cell_measurement_theta_min      2.833
_cell_volume                     2205.5(8)
_computing_cell_refinement       'SAINT v7.68A (Bruker, 2009)'
_computing_data_reduction        'SAINT v7.68A (Bruker, 2009)'
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      130
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.999
_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  0.0631
_diffrn_reflns_av_unetI/netI     0.0679
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       33
_diffrn_reflns_limit_h_min       -33
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       8
_diffrn_reflns_limit_l_min       -8
_diffrn_reflns_number            17312
_diffrn_reflns_point_group_measured_fraction_full 0.988
_diffrn_reflns_point_group_measured_fraction_max 0.984
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.519
_diffrn_reflns_theta_min         1.753
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.086
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.5954
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.1074 before and 0.0616 after correction.
The Ratio of minimum to maximum transmission is 0.7986.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.287
_exptl_crystal_description       plate
_exptl_crystal_F_000             904
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.01
_refine_diff_density_max         0.203
_refine_diff_density_min         -0.193
_refine_diff_density_rms         0.044
_refine_ls_abs_structure_details
;
 Flack x determined using 1318 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.4(10)
_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     292
_refine_ls_number_reflns         4997
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.036
_refine_ls_R_factor_all          0.0816
_refine_ls_R_factor_gt           0.0557
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0427P)^2^+0.6818P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1110
_refine_ls_wR_factor_ref         0.1218
_reflns_Friedel_coverage         0.812
_reflns_Friedel_fraction_full    0.974
_reflns_Friedel_fraction_max     0.967
_reflns_number_gt                3761
_reflns_number_total             4997
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja5b12522_si_002.cif
_cod_data_source_block           5
_cod_database_code               4129983
_shelxl_version_number           2014-3
_shelx_estimated_absorpt_t_max   0.999
_shelx_estimated_absorpt_t_min   0.979
_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.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B)
2.b Aromatic/amide H refined with riding coordinates:
 C10(H10), C11(H11), C12(H12), C13(H13), C14(H14), C16(H16), C17(H17),
 C18(H18), C19(H19), C20(H20), C23(H23), C24(H24), C26(H26), C27(H27)
2.c Idealised Me refined as rotating group:
 C4(H4A,H4B,H4C), C7(H7A,H7B,H7C), C8(H8A,H8B,H8C)
;
_shelx_res_checksum              54045
_shelx_hkl_checksum              64469
_olex2_submission_special_instructions 'No special instructions were received'