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_4102780
_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         'C20 H16 Cl N '
_chemical_formula_sum            'C20 H16 Cl N'
_chemical_formula_weight         305.81
_space_group_IT_number           4
_symmetry_cell_setting           monoclinic
_symmetry_Int_Tables_number      4
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_cell_angle_alpha                90.0000
_cell_angle_beta                 90.442(3)
_cell_angle_gamma                90.0000
_cell_formula_units_Z            2
_cell_length_a                   11.6476(14)
_cell_length_b                   5.0598(8)
_cell_length_c                   13.0466(16)
_cell_measurement_reflns_used    4265
_cell_measurement_temperature    173.1
_cell_measurement_theta_max      27.4
_cell_measurement_theta_min      3.1
_cell_volume                     768.87(18)
_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    SHELXS97
_diffrn_ambient_temperature      173.1
_diffrn_detector_area_resol_mean 10.00
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_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  0.086
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       6
_diffrn_reflns_limit_k_min       -6
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            7519
_diffrn_reflns_theta_full        27.45
_diffrn_reflns_theta_max         27.45
_exptl_absorpt_coefficient_mu    0.244
_exptl_absorpt_correction_T_max  0.988
_exptl_absorpt_correction_T_min  0.815
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_process_details
;
    Higashi, T. (1999). Program for Absorption Correction.
    Rigaku Corporation, Tokyo, Japan.
;
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.321
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       needle
_exptl_crystal_F_000             320.00
_exptl_crystal_size_max          0.45
_exptl_crystal_size_mid          0.10
_exptl_crystal_size_min          0.05
_refine_diff_density_max         1.00
_refine_diff_density_min         -1.08
_refine_ls_abs_structure_details
'Flack, H. D. (1983), Acta Cryst. A39, 876-881.  1503 Friedel Pairs'
_refine_ls_abs_structure_Flack   0.10(11)
_refine_ls_extinction_coef       139(18)
_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     217
_refine_ls_number_reflns         3457
_refine_ls_R_factor_gt           0.0560
_refine_ls_shift/su_max          0.0000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     'w = 1/[0.8340\s(Fo^2^)]/(4Fo^2^)'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_ref         0.1344
_reflns_number_gt                1578
_reflns_number_total             3457
_reflns_threshold_expression     F^2^>2.0\s(F^2^)
_cod_data_source_file            ja1047494_si_002_2.cif
_cod_data_source_block           '_C20H16ClN'
_cod_original_cell_volume        768.86(17)
_cod_original_formula_sum        'C20 H16 Cl N '
_cod_database_code               4102780