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_4102782
_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         'C88 H64 Cl2 Cu2 P4 '
_chemical_formula_sum            'C88 H64 Cl2 Cu2 P4'
_chemical_formula_weight         1443.37
_space_group_IT_number           96
_symmetry_cell_setting           tetragonal
_symmetry_Int_Tables_number      96
_symmetry_space_group_name_Hall  'P 4nw 2abw'
_symmetry_space_group_name_H-M   'P 43 21 2'
_cell_angle_alpha                90.0000
_cell_angle_beta                 90.0000
_cell_angle_gamma                90.0000
_cell_formula_units_Z            4
_cell_length_a                   13.8976(4)
_cell_length_b                   13.8976(4)
_cell_length_c                   35.5493(13)
_cell_measurement_reflns_used    24126
_cell_measurement_temperature    173.1
_cell_measurement_theta_max      27.5
_cell_measurement_theta_min      3.1
_cell_volume                     6866.1(4)
_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 0.996
_diffrn_measured_fraction_theta_max 0.996
_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  0.156
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       46
_diffrn_reflns_limit_l_min       -45
_diffrn_reflns_number            53658
_diffrn_reflns_theta_full        27.48
_diffrn_reflns_theta_max         27.48
_exptl_absorpt_coefficient_mu    0.839
_exptl_absorpt_correction_T_max  0.845
_exptl_absorpt_correction_T_min  0.651
_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    1.396
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             2976.00
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.20
_refine_diff_density_max         2.92
_refine_diff_density_min         -3.40
_refine_ls_abs_structure_details
'Flack, H. D. (1983), Acta Cryst. A39, 876-881.  3333 Friedel Pairs'
_refine_ls_abs_structure_Flack   0.02(2)
_refine_ls_extinction_coef       522(50)
_refine_ls_extinction_method
'Larson (1970) Crystallographic Computing eq. 22'
_refine_ls_goodness_of_fit_ref   1.000
_refine_ls_hydrogen_treatment    refall
_refine_ls_number_parameters     467
_refine_ls_number_reflns         7856
_refine_ls_R_factor_gt           0.0451
_refine_ls_shift/su_max          0.0000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w = 1/[0.0002Fo^2^ + 0.3755\s(Fo^2^)]/(4Fo^2^)'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_ref         0.1290
_reflns_number_gt                2865
_reflns_number_total             7856
_reflns_threshold_expression     F^2^>2.0\s(F^2^)
_cod_data_source_file            ja1047494_si_002_4.cif
_cod_data_source_block           '_[CuCl(BINAP)]2'
_cod_original_formula_sum        'C88 H64 Cl2 Cu2 P4 '
_cod_database_code               4102782