Mechanistic Studies on the Catalytic Asymmetric Mannich-Type Reaction with Dihydroisoquinolines and Development of Oxidative Mannich-Type Reactions Starting from Tetrahydroisoquinolines
Christian Dubs; Yoshitaka Hamashima; Naoki Sasamoto; Thomas M. Seidel; Shoko Suzuki; Daisuke Hashizume; Mikiko Sodeoka; Journal of Organic Chemistry 73 (2008) 5859–5871; doi:10.1021/jo800800y

data_4023587
_publ_section_title
;
 Mechanistic Studies on the Catalytic Asymmetric Mannich-Type
 Reaction with Dihydroisoquinolines and Development of Oxidative
 Mannich-Type Reactions Starting from Tetrahydroisoquinolines
;
_journal_name_full               'Journal of Organic Chemistry'
_journal_page_first              5859
_journal_page_last               5871
_journal_paper_doi               10.1021/jo800800y
_journal_volume                  73
_journal_year                    2008
_chemical_absolute_configuration syn
_chemical_formula_moiety         'C16 H19 N O5'
_chemical_formula_sum            'C16 H19 N O5'
_chemical_formula_weight         305.32
_space_group_IT_number           4
_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   difmap
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-97
_cell_angle_alpha                90
_cell_angle_beta                 99.373(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.675(2)
_cell_length_b                   15.232(4)
_cell_length_c                   11.263(3)
_cell_measurement_reflns_used    5690
_cell_measurement_temperature    100
_cell_measurement_theta_max      32.5145
_cell_measurement_theta_min      1.8325
_cell_volume                     1468.5(6)
_computing_cell_refinement       'CrystalClear (Rigaku/MSC Inc., 2005)'
_computing_data_collection       'CrystalClear (Rigaku/MSC Inc., 2005)'
_computing_data_reduction        'CrystalClear (Rigaku/MSC Inc., 2005)'
_computing_molecular_graphics    'ORTEP-3 for Windows'
_computing_publication_material  SHELXL-97
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_structure_solution    SIR2004
_diffrn_ambient_temperature      100
_diffrn_detector_area_resol_mean 28.5714
_diffrn_measured_fraction_theta_full 0.992
_diffrn_measured_fraction_theta_max 0.992
_diffrn_measurement_details
;
scan:
    Number of images: 60
               Slice: -50.0000 - -20.0000
         Image width: 0.5000
            Exp time: 2.0000
       Rotation axis: Omega
               Omega: 0.0000
                 Chi: 0.0000
                 Phi: 0.0000
                 XTD: 40.0675
              2theta: 20.0736
scan:
    Number of images: 360
               Slice: -70.0000 - 110.0000
         Image width: 0.5000
            Exp time: 2.0000
       Rotation axis: Omega
               Omega: 0.0000
                 Chi: 30.0000
                 Phi: 0.0000
                 XTD: 40.0675
              2theta: 20.0736

;
_diffrn_measurement_device_details
;
AFC8: Eulerian 3-circle
;
_diffrn_measurement_device_type  'Rigaku AFC-8 with Saturn70 CCD'
_diffrn_measurement_method       \w-scan
_diffrn_orient_matrix_type       d*Trek
_diffrn_orient_matrix_UB_11      -0.1018
_diffrn_orient_matrix_UB_12      -0.0455
_diffrn_orient_matrix_UB_13      -0.0350
_diffrn_orient_matrix_UB_21      0.0310
_diffrn_orient_matrix_UB_22      -0.0327
_diffrn_orient_matrix_UB_23      -0.0477
_diffrn_orient_matrix_UB_31      -0.0009
_diffrn_orient_matrix_UB_32      -0.0745
_diffrn_orient_matrix_UB_33      0.0505
_diffrn_radiation_monochromator  confocal
_diffrn_radiation_source         'fine-focus rotating anode'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0403
_diffrn_reflns_av_sigmaI/netI    0.0727
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            8921
_diffrn_reflns_theta_full        30.07
_diffrn_reflns_theta_max         30.07
_diffrn_reflns_theta_min         1.83
_diffrn_source_current           24
_diffrn_source_power             1.2
_diffrn_source_voltage           50
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.103
_exptl_absorpt_correction_T_max  0.9972
_exptl_absorpt_correction_T_min  0.8434
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrystalClear (Rigaku/MSC Inc., 2005)
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.381
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             648
_exptl_crystal_size_max          0.42
_exptl_crystal_size_mid          0.21
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.253
_refine_diff_density_min         -0.288
_refine_diff_density_rms         0.062
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.018
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     415
_refine_ls_number_reflns         4434
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.018
_refine_ls_R_factor_all          0.0646
_refine_ls_R_factor_gt           0.0489
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0490P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0970
_refine_ls_wR_factor_ref         0.1085
_reflns_number_gt                3455
_reflns_number_total             4434
_reflns_threshold_expression     I>2\s(I)
_cod_data_source_file            jo800800y-File003.cif
_cod_data_source_block           lactam
_cod_original_sg_symbol_H-M      'P 21'
_cod_database_code               4023587