Catalytic Asymmetric Syntheses of Quinolizidines by Dirhodium-Catalyzed Dearomatization of Isoquinolinium/Pyridinium Methylides-The Role of Catalyst and Carbene Source
Xichen Xu; Peter Y. Zavalij; Michael P. Doyle; Journal of the American Chemical Society 135 (2013) 12439–12447; doi:10.1021/ja406482q

data_4120344
_publ_section_title
;
 Catalytic Asymmetric Syntheses of Quinolizidines by Dirhodium-Catalyzed
 Dearomatization of Isoquinolinium/Pyridinium Methylides-The Role of
 Catalyst and Carbene Source
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              12439
_journal_page_last               12447
_journal_paper_doi               10.1021/ja406482q
_journal_volume                  135
_journal_year                    2013
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C29 H31 N3 O3 Si'
_chemical_formula_sum            'C29 H31 N3 O3 Si'
_chemical_formula_weight         497.66
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_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   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method           'SHELXL-2012 & ZCIF'
_cell_angle_alpha                90
_cell_angle_beta                 92.8103(14)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.0538(14)
_cell_length_b                   6.3146(7)
_cell_length_c                   32.590(3)
_cell_measurement_reflns_used    8869
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      28.1
_cell_measurement_theta_min      2.4
_cell_volume                     2683.1(5)
_computing_cell_refinement       Apex2
_computing_data_collection       'Apex2 (Bruker, 2010)'
_computing_data_reduction        Apex2
_computing_molecular_graphics    'XSHEL (Bruker, 2004)'
_computing_publication_material  'Apex2, SHELXL-2012'
_computing_structure_refinement  'ShelXL-2012 (Sheldrick, 2012)'
_computing_structure_solution    'ShelXS-97 (Sheldrick, 2008)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'CCD area detector'
_diffrn_detector_area_resol_mean 8.333
_diffrn_detector_type            'Bruker Smart Apex II'
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_device_type  'three-circle diffractometer'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_measurement_specimen_support 'MiTeGen loop'
_diffrn_orient_matrix_type       standard
_diffrn_orient_matrix_UB_11      0.0443838
_diffrn_orient_matrix_UB_12      -0.1265199
_diffrn_orient_matrix_UB_13      -0.0041933
_diffrn_orient_matrix_UB_21      -0.0163708
_diffrn_orient_matrix_UB_22      0.0074539
_diffrn_orient_matrix_UB_23      -0.0302644
_diffrn_orient_matrix_UB_31      0.0603745
_diffrn_orient_matrix_UB_32      0.0949588
_diffrn_orient_matrix_UB_33      -0.0032100
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0369
_diffrn_reflns_av_unetI/netI     0.0506
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_l_max       38
_diffrn_reflns_limit_l_min       -38
_diffrn_reflns_number            22695
_diffrn_reflns_point_group_measured_fraction_full 0.989
_diffrn_reflns_point_group_measured_fraction_max 0.989
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         24.998
_diffrn_reflns_theta_min         2.049
_diffrn_source                   'sealed tube'
_diffrn_source_current           30.00
_diffrn_source_voltage           50.00
_exptl_absorpt_coefficient_mu    0.122
_exptl_absorpt_correction_T_max  0.993
_exptl_absorpt_correction_T_min  0.809
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SADABS (Sheldrick, 2008)'
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.232
_exptl_crystal_description       plate
_exptl_crystal_F_000             1056
_exptl_crystal_id                'Doyle-XU 12-07-12'
_exptl_crystal_size_max          0.34
_exptl_crystal_size_mid          0.24
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.587
_refine_diff_density_min         -0.296
_refine_diff_density_rms         0.052
_refine_ls_abs_structure_details
;
 Flack x determined using 3563 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   0.03(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.000
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     660
_refine_ls_number_reflns         9377
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.000
_refine_ls_R_factor_all          0.0542
_refine_ls_R_factor_gt           0.0493
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
;
 w=1/[\s^2^(Fo^2^)+(0.0100P)^2^+3.9600P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1019
_refine_ls_wR_factor_ref         0.1045
_reflns_Friedel_coverage         0.807
_reflns_Friedel_fraction_full    0.981
_reflns_Friedel_fraction_max     0.981
_reflns_number_gt                8656
_reflns_number_total             9377
_reflns_threshold_expression     'I > 2\s(I)'
_iucr_refine_instructions_details 'See _shelx_res_file'
_cod_data_source_file            ja406482q_si_002.cif
_cod_data_source_block           2371
_cod_original_cell_volume        2683.2(5)
_cod_database_code               4120344
_shelx_estimated_absorpt_t_min   0.960
_shelx_estimated_absorpt_t_max   0.993