Highly diastereo- and enantioselective copper-catalyzed propargylic alkylation of acyclic ketone enamines for the construction of two vicinal stereocenters
De-Yang Zhang; Fu-Lin Zhu; Ya-Hui Wang; Xin-Hu Hu; Song Chen; Chuan-Jin Hou; Xiang-Ping Hu; Chem.Commun. 50 (2014) 14459–; doi:10.1039/C4cc06863G

data_7115951
_publ_section_title
;
 Highly diastereo- and enantioselective copper-catalyzed propargylic
 alkylation of acyclic ketone enamines for the construction of two vicinal
 stereocenters
;
_journal_name_full               Chem.Commun.
_journal_page_first              14459
_journal_paper_doi               10.1039/C4cc06863G
_journal_volume                  50
_journal_year                    2014
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C19 H17 Br O2'
_chemical_formula_sum            'C19 H17 Br O2'
_chemical_formula_weight         357.23
_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
_audit_creation_date             2014-04-22
_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                   5.5798(14)
_cell_length_b                   15.675(4)
_cell_length_c                   19.082(5)
_cell_measurement_reflns_used    4309
_cell_measurement_temperature    173.1500
_cell_measurement_theta_max      27.4686
_cell_measurement_theta_min      2.4991
_cell_volume                     1669.0(7)
_computing_cell_refinement       'CrystalClear (Rigaku Inc., 2007)'
_computing_data_collection       'CrystalClear (Rigaku Inc., 2007)'
_computing_data_reduction        'CrystalClear (Rigaku Inc., 2007)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2013)'
_computing_structure_solution
;
'XS (Sheldrick, 2013)'
;
_diffrn_ambient_temperature      173.1500
_diffrn_detector_area_resol_mean 28.5714
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device
;
Saturn724+ (2x2 bin mode)
;
_diffrn_measurement_device_details
;
AFC10: Fixed Chi 2 circle
;
_diffrn_measurement_device_type  'Saturn724+ CCD'
_diffrn_measurement_method       '\w scans at fixed \c = 45\%'
_diffrn_orient_matrix_type       d*Trek
_diffrn_orient_matrix_UB_11      -0.0380
_diffrn_orient_matrix_UB_12      -0.1716
_diffrn_orient_matrix_UB_13      0.0350
_diffrn_orient_matrix_UB_21      -0.0375
_diffrn_orient_matrix_UB_22      -0.0022
_diffrn_orient_matrix_UB_23      -0.0516
_diffrn_orient_matrix_UB_31      0.0409
_diffrn_orient_matrix_UB_32      -0.0150
_diffrn_orient_matrix_UB_33      -0.0291
_diffrn_radiation_detector       CCD
_diffrn_radiation_monochromator  'Graphite Monochromator'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0572
_diffrn_reflns_av_unetI/netI     0.0529
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            10540
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         27.475
_diffrn_reflns_theta_min         3.364
_diffrn_source                   'Sealed Tube'
_diffrn_source_current           30.0000
_diffrn_source_power             1.5000
_diffrn_source_voltage           50.0000
_exptl_absorpt_coefficient_mu    2.467
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.5550
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'CrystalClear (Rigaku Inc., 2007)'
_exptl_crystal_colour            Colorless
_exptl_crystal_density_diffrn    1.422
_exptl_crystal_description       rod
_exptl_crystal_F_000             728
_exptl_crystal_size_max          0.34
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.469
_refine_diff_density_min         -0.341
_refine_diff_density_rms         0.066
_refine_ls_abs_structure_details
;
 Flack x determined using 1211 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   0.024(11)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.121
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     201
_refine_ls_number_reflns         3797
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.121
_refine_ls_R_factor_all          0.0542
_refine_ls_R_factor_gt           0.0483
_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^)+(0.0375P)^2^+0.5150P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1008
_refine_ls_wR_factor_ref         0.1048
_reflns_Friedel_coverage         0.710
_reflns_Friedel_fraction_full    0.993
_reflns_Friedel_fraction_max     0.986
_reflns_number_gt                3477
_reflns_number_total             3797
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c4cc06863g2.cif
_cod_data_source_block           sa3346
_cod_original_cell_volume        1669.1(8)
_cod_database_code               7115951
_shelxl_version_number           2013-4
_diffrn_number_total             2250
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C1(H1), C2(H2)
2.b Aromatic/amide H refined with riding coordinates:
 C5(H5), C6(H6), C8(H8), C9(H9), C14(H14), C15(H15), C17(H17), C18(H18)
2.c Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C), C19(H19A,H19B,H19C)
2.d :
 C12(H12)
;
_shelx_res_checksum              59937
_shelx_hkl_checksum              96735