NHC-Cu-Catalyzed Addition of Propargylboron Reagents to Phosphinoylimines. Enantioselective Synthesis of Trimethylsilyl-Substituted Homoallenylamides and Application to the Synthesis of S-(-)-Cyclooroidin.
Mszar, Nicholas W.; Haeffner, Fredrik; Hoveyda, Amir H.; Journal of the American Chemical Society 136 (2014) 3362–3365; doi:10.1021/ja500373s

data_4121496
_publ_section_title
;
 NHC-Cu-Catalyzed Addition of Propargylboron Reagents to
 Phosphinoylimines. Enantioselective Synthesis of
 Trimethylsilyl-Substituted Homoallenylamides and Application to the
 Synthesis of S-(-)-Cyclooroidin.
;
_journal_issue                   9
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              3362
_journal_page_last               3365
_journal_paper_doi               10.1021/ja500373s
_journal_volume                  136
_journal_year                    2014
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C25 H27 Br N O P Si'
_chemical_formula_sum            'C25 H27 Br N O P Si'
_chemical_formula_weight         496.44
_chemical_name_systematic
;
 ?
;
_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   mixed
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-2013
_cell_angle_alpha                90
_cell_angle_beta                 96.599(3)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   19.8739(8)
_cell_length_b                   10.2459(5)
_cell_length_c                   24.6435(9)
_cell_measurement_reflns_used    9966
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      68.47
_cell_measurement_theta_min      3.03
_cell_volume                     4984.8(4)
_computing_cell_refinement       'SAINT (Bruker, 2013)'
_computing_data_collection       'APEX2 (Bruker, 2013)'
_computing_data_reduction        'SAINT (Bruker, 2013)'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'
_computing_structure_refinement  'SHELXL-2013 (Sheldrick, 2013)'
_computing_structure_solution    'SHELXL-2013 (Sheldrick, 2013)'
_diffrn_ambient_temperature      100(2)
_diffrn_measured_fraction_theta_full 0.968
_diffrn_measured_fraction_theta_max 0.961
_diffrn_measurement_device_type  'Bruker Kappa DUO CCD diffractometer'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  mirrors
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0895
_diffrn_reflns_av_unetI/netI     0.0913
_diffrn_reflns_Laue_measured_fraction_full 0.968
_diffrn_reflns_Laue_measured_fraction_max 0.961
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            49707
_diffrn_reflns_point_group_measured_fraction_full 0.795
_diffrn_reflns_point_group_measured_fraction_max 0.788
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         68.225
_diffrn_reflns_theta_min         1.805
_diffrn_source                   'microfocus sealed tube'
_diffrn_source_type              'Incoatec I\uS'
_exptl_absorpt_coefficient_mu    3.433
_exptl_absorpt_correction_T_max  0.7532
_exptl_absorpt_correction_T_min  0.6241
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
Sheldrick, G.M. (2013). SADABS. Bruker AXS Inc. Madison, WI USA.
;
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.323
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    none
_exptl_crystal_description       block
_exptl_crystal_F_000             2048
_exptl_crystal_size_max          0.140
_exptl_crystal_size_mid          0.100
_exptl_crystal_size_min          0.060
_refine_diff_density_max         1.293
_refine_diff_density_min         -0.863
_refine_diff_density_rms         0.105
_refine_ls_abs_structure_details
;
 Flack x determined using 2783 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   0.011(13)
_refine_ls_extinction_coef       na
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.013
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1104
_refine_ls_number_reflns         14390
_refine_ls_number_restraints     314
_refine_ls_restrained_S_all      1.005
_refine_ls_R_factor_all          0.0999
_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^)+(0.0938P)^2^+3.3913P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1530
_refine_ls_wR_factor_ref         0.1717
_reflns_Friedel_coverage         0.547
_reflns_Friedel_fraction_full    0.600
_reflns_Friedel_fraction_max     0.593
_reflns_number_gt                10320
_reflns_number_total             14390
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja500373s_si_002.cif
_cod_data_source_block           C25H27BrNOPSi
_cod_depositor_comments
;
The following automatic conversions were performed:

'_exptl_crystal_density_meas' value 'not measured' was changed to '?'
- the value is perceived as not measured.

Automatic conversion script
Id: cif_fix_values 3008 2015-01-20 13:52:24Z robertas 
;
_cod_database_code               4121496
_shelx_estimated_absorpt_t_min   0.645
_shelx_estimated_absorpt_t_max   0.821
_shelxl_version_number           2013-2
_shelx_res_checksum              18545
_shelx_hkl_checksum              61113