Copper-Catalyzed Enantioselective Propargylic Amination of Propargylic Esters with Amines: Copper-Allenylidene Complexes as Key Intermediates
Gaku Hattori; Ken Sakata; Hiroshi Matsuzawa; Yoshiaki Tanabe; Yoshihiro Miyake; Yoshiaki Nishibayashi; Journal of the American Chemical Society 132 (2010) 10592–10608; doi:10.1021/ja1047494

data_4102779
_publ_contact_author_email       ynishiba@sogo.t.u-tokyo.ac.jp
_publ_contact_author_fax         +81-3-5841-1175
_publ_contact_author_name        'Yoshiaki Nishibayashi'
_publ_contact_author_phone       +81-3-5841-7708
_publ_section_title
;
 Copper-Catalyzed Enantioselective Propargylic Amination of Propargylic
 Esters with Amines: Copper-Allenylidene Complexes as Key Intermediates
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              10592
_journal_page_last               10608
_journal_paper_doi               10.1021/ja1047494
_journal_volume                  132
_journal_year                    2010
_chemical_absolute_configuration 'CHOOSE rm ad rmad syn or unk'
_chemical_formula_moiety         'C106 H102 Cl4 Cu2 O4 P4 '
_chemical_formula_sum            'C106 H102 Cl4 Cu2 O4 P4'
_chemical_formula_weight         1832.77
_space_group_IT_number           152
_symmetry_cell_setting           trigonal
_symmetry_Int_Tables_number      152
_symmetry_space_group_name_Hall  'P 31 2"'
_symmetry_space_group_name_H-M   'P 31 2 1'
_cell_angle_alpha                90.0000
_cell_angle_beta                 90.0000
_cell_angle_gamma                120.0000
_cell_formula_units_Z            3
_cell_length_a                   18.9573(8)
_cell_length_b                   18.9573(8)
_cell_length_c                   25.3920(9)
_cell_measurement_reflns_used    53206
_cell_measurement_temperature    173.1
_cell_measurement_theta_max      27.4
_cell_measurement_theta_min      3.2
_cell_volume                     7902.8(5)
_computing_cell_refinement       PROCESS-AUTO
_computing_data_collection       PROCESS-AUTO
_computing_data_reduction        CrystalStructure
_computing_publication_material  'CrystalStructure 3.8'
_computing_structure_refinement  CRYSTALS
_computing_structure_solution    SIR97
_diffrn_ambient_temperature      173.1
_diffrn_detector_area_resol_mean 10.00
_diffrn_measured_fraction_theta_full 1.024
_diffrn_measured_fraction_theta_max 1.024
_diffrn_measurement_device_type  'Rigaku RAXIS-RAPID'
_diffrn_measurement_method       \w
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71075
_diffrn_reflns_av_R_equivalents  0.053
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            77957
_diffrn_reflns_theta_full        27.46
_diffrn_reflns_theta_max         27.46
_exptl_absorpt_coefficient_mu    0.612
_exptl_absorpt_correction_T_max  0.736
_exptl_absorpt_correction_T_min  0.237
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
    Higashi, T. (1995). Program for Absorption Correction.
    Rigaku Corporation, Tokyo, Japan.
;
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    1.155
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             2868.00
_exptl_crystal_size_max          0.70
_exptl_crystal_size_mid          0.50
_exptl_crystal_size_min          0.50
_refine_diff_density_max         0.87
_refine_diff_density_min         -0.83
_refine_ls_abs_structure_details
'Flack, H. D. (1983), Acta Cryst. A39, 876-881.  5470 Friedel Pairs'
_refine_ls_abs_structure_Flack   -0.001(9)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.000
_refine_ls_hydrogen_treatment    refall
_refine_ls_number_parameters     582
_refine_ls_number_reflns         11781
_refine_ls_R_factor_gt           0.0408
_refine_ls_shift/su_max          0.0000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     'w = 1/[0.7950\s(Fo^2^)]/(4Fo^2^)'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_ref         0.0856
_reflns_number_gt                7237
_reflns_number_total             11781
_reflns_threshold_expression     F^2^>2.0\s(F^2^)
_cod_data_source_file            ja1047494_si_002_1.cif
_cod_data_source_block           '_[Cu(CCTol)(Cl-MeO-BIPHEP)]2.2C6H14'
_cod_original_formula_sum        'C106 H102 Cl4 Cu2 O4 P4 '
_cod_database_code               4102779