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_4023586
_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 rmad
_chemical_formula_moiety         'C48 H44 F6 O10 P2 Pd S2, 3(C D Cl3)'
_chemical_formula_sum            'C51 H44 Cl9 D3 F6 O10 P2 Pd S2'
_chemical_formula_weight         1488.44
_space_group_IT_number           19
_symmetry_cell_setting           orthorhombic
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-97
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.0672(14)
_cell_length_b                   15.2049(18)
_cell_length_c                   33.606(4)
_cell_measurement_reflns_used    18889
_cell_measurement_temperature    90
_cell_measurement_theta_max      31.4203
_cell_measurement_theta_min      1.7930
_cell_volume                     6166.0(13)
_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 (Sheldrick, 1997)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_structure_solution    SIR-92
_diffrn_ambient_temperature      90
_diffrn_detector_area_resol_mean 28.5714
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_details
;
scan:
        Number of images: 360
                   Slice: -60.0000 - 120.0000
             Image width: 0.5000
                Exp time: 16.0000
           Rotation axis: Omega
                   Omega: 0.0000
                     Chi: 0.0000
                     Phi: 0.0000
                     XTD: 59.8505
                  2theta: 30.0792
scan:
        Number of images: 360
                   Slice: -60.0000 - 120.0000
             Image width: 0.5000
                Exp time: 16.0000
           Rotation axis: Omega
                   Omega: 0.0000
                     Chi: 50.0000
                     Phi: 45.0000
                     XTD: 59.8505
                  2theta: 30.0792
scan:
        Number of images: 360
                   Slice: -60.0000 - 120.0000
             Image width: 0.5000
                Exp time: 16.0000
           Rotation axis: Omega
                   Omega: 0.0000
                     Chi: 50.0000
                     Phi: 90.0000
                     XTD: 59.8505
                  2theta: 30.0792
scan:
        Number of images: 360
                   Slice: -60.0000 - 120.0000
             Image width: 0.5000
                Exp time: 16.0000
           Rotation axis: Omega
                   Omega: 0.0000
                     Chi: 50.0000
                     Phi: 180.0000
                     XTD: 59.8505
                  2theta: 30.0792
scan:
        Number of images: 360
                   Slice: -60.0000 - 120.0000
             Image width: 0.5000
                Exp time: 16.0000
           Rotation axis: Omega
                   Omega: 0.0000
                     Chi: 50.0000
                     Phi: 270.0000
                     XTD: 59.8505
                  2theta: 30.0792

;
_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      0.0811
_diffrn_orient_matrix_UB_12      0.0106
_diffrn_orient_matrix_UB_13      0.0130
_diffrn_orient_matrix_UB_21      0.0114
_diffrn_orient_matrix_UB_22      -0.0613
_diffrn_orient_matrix_UB_23      -0.0209
_diffrn_orient_matrix_UB_31      0.0032
_diffrn_orient_matrix_UB_32      0.0101
_diffrn_orient_matrix_UB_33      -0.0278
_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  0.0394
_diffrn_reflns_av_sigmaI/netI    0.0269
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       47
_diffrn_reflns_limit_l_min       -47
_diffrn_reflns_number            116652
_diffrn_reflns_theta_full        30.04
_diffrn_reflns_theta_max         30.04
_diffrn_reflns_theta_min         1.79
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.882
_exptl_absorpt_correction_T_max  0.9474
_exptl_absorpt_correction_T_min  0.7089
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_process_details
;
Higashi, T. (1999). Numabs-Numerical Absorption Correction, 
Rigaku Corporation, Tokyo, Japan.
;
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    1.603
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       needle
_exptl_crystal_F_000             2992
_exptl_crystal_size_max          0.57
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.921
_refine_diff_density_min         -0.676
_refine_diff_density_rms         0.070
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   -0.020(13)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.071
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     757
_refine_ls_number_reflns         18030
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.071
_refine_ls_R_factor_all          0.0358
_refine_ls_R_factor_gt           0.0344
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0287P)^2^+5.6535P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0757
_refine_ls_wR_factor_ref         0.0766
_reflns_number_gt                17529
_reflns_number_total             18030
_reflns_threshold_expression     I>2\s(I)
_cod_data_source_file            jo800800y-File002.cif
_cod_data_source_block           Pd-complex
_cod_depositor_comments
;
The following automatic conversions were performed:
'_exptl_absorpt_correction_type' value 'Numerical' changed to 'numerical'
according to '/home/saulius/struct/CIF-dictionaries/cif_core.dic'
dictionary named 'cif_core.dic' version 2.4.1 from 2010-06-29.

Automatic conversion script
Id: cif_fix_enum 1527 2010-12-29 10:47:43Z saulius 
;
_cod_database_code               4023586