Highly Enantioselective Synthesis of Propargyl Amides through Rh-Catalyzed Asymmetric Hydroalkynylation of Enamides: Scope, Mechanism, and Origin of Selectivity.
Bai, Xiao-Yan; Zhang, Wen-Wen; Li, Qian; Li, Bi-Jie; Journal of the American Chemical Society  (2017) –; doi:10.1021/jacs.7b12054

data_4126899
_publ_section_title
;
 Highly Enantioselective Synthesis of Propargyl Amides through
 Rh-Catalyzed Asymmetric Hydroalkynylation of Enamides: Scope, Mechanism,
 and Origin of Selectivity.
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_paper_doi               10.1021/jacs.7b12054
_journal_year                    2017
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C14 H16 Br N O'
_chemical_formula_sum            'C14 H16 Br N O'
_chemical_formula_weight         294.19
_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
_audit_creation_method           SHELXL-2014/7
_cell_angle_alpha                90
_cell_angle_beta                 90.212(4)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   4.8610(2)
_cell_length_b                   9.8176(4)
_cell_length_c                   14.4748(5)
_cell_measurement_reflns_used    3927
_cell_measurement_temperature    173.0(1)
_cell_measurement_theta_max      76.8
_cell_measurement_theta_min      5.4
_cell_volume                     690.78(5)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_structure_solution    'Bruker SHELXTL'
_diffrn_ambient_temperature      173.0(1)
_diffrn_detector_area_resol_mean 5.2137
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, AtlasS2'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0477
_diffrn_reflns_av_unetI/netI     0.0480
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            7100
_diffrn_reflns_point_group_measured_fraction_full 0.966
_diffrn_reflns_point_group_measured_fraction_max 0.958
_diffrn_reflns_theta_full        74.500
_diffrn_reflns_theta_max         76.844
_diffrn_reflns_theta_min         5.444
_exptl_absorpt_coefficient_mu    3.922
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.679
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.414
_exptl_crystal_density_meas      ?
_exptl_crystal_description       needle
_exptl_crystal_F_000             300
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.323
_refine_diff_density_min         -0.413
_refine_diff_density_rms         0.062
_refine_ls_abs_structure_details
; 
 Flack x determined using 1098 quotients [(I+)-(I-)]/[(I+)+(I-)] 
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259). 
;
_refine_ls_abs_structure_Flack   0.03(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.989
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     159
_refine_ls_number_reflns         2791
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      0.989
_refine_ls_R_factor_all          0.0438
_refine_ls_R_factor_gt           0.0411
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0010P)^2^+1.5000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0936
_refine_ls_wR_factor_ref         0.0956
_reflns_Friedel_coverage         0.814
_reflns_Friedel_fraction_full    0.929
_reflns_Friedel_fraction_max     0.915
_reflns_number_gt                2638
_reflns_number_total             2791
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b12054_si_002.cif
_cod_data_source_block           try
_cod_depositor_comments
;
The following automatic conversions were performed:

'_exptl_crystal_density_meas' value 'none' was changed to '?' - the
value is perceived as not measured.

Automatic conversion script
Id: cif_fix_values 4973 2017-02-22 13:04:09Z antanas 
;
_cod_database_code               4126899
_shelx_shelxl_version_number     2014/7
_shelx_res_checksum              47396
_shelx_hkl_checksum              75581