Desymmetrization of cyclohexadienones via cinchonine derived thiourea-catalyzed enantioselective aza-Michael reaction and total synthesis of (-)-Mesembrine
Gu, Qing; You, Shu-Li; Chemical Science 2 (2011) 1519–; doi:10.1039/c1sc00083g

data_1515600
_publ_section_title
;
 Desymmetrization of cyclohexadienones via cinchonine derived
 thiourea-catalyzed enantioselective aza-Michael reaction and total
 synthesis of (-)-Mesembrine
;
_journal_issue                   8
_journal_name_full               'Chemical Science'
_journal_page_first              1519
_journal_paper_doi               10.1039/c1sc00083g
_journal_volume                  2
_journal_year                    2011
_chemical_absolute_configuration ad
_chemical_formula_sum            'C22 H20 Br N O5 S'
_chemical_formula_weight         490.36
_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                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   10.3614(8)
_cell_length_b                   11.1748(9)
_cell_length_c                   18.7204(16)
_cell_measurement_reflns_used    2218
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      39.281
_cell_measurement_theta_min      4.493
_cell_volume                     2167.6(3)
_computing_cell_refinement       'Bruker SMART'
_computing_data_collection       'Bruker SMART'
_computing_data_reduction        'Bruker SHELXTL'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_diffrn_ambient_temperature      293(2)
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0535
_diffrn_reflns_av_sigmaI/netI    0.1019
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            13168
_diffrn_reflns_theta_full        27.50
_diffrn_reflns_theta_max         27.50
_diffrn_reflns_theta_min         2.12
_exptl_absorpt_coefficient_mu    2.026
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.5316
_exptl_absorpt_correction_type   empirical
_exptl_absorpt_process_details   sadabs
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.503
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       prisamtic
_exptl_crystal_F_000             1000
_exptl_crystal_size_max          0.305
_exptl_crystal_size_mid          0.229
_exptl_crystal_size_min          0.170
_refine_diff_density_max         0.472
_refine_diff_density_min         -0.232
_refine_diff_density_rms         0.039
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.029(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.848
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     272
_refine_ls_number_reflns         4935
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      0.848
_refine_ls_R_factor_all          0.0829
_refine_ls_R_factor_gt           0.0364
_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
[0.00000+1.00000exp(2.00(sin\q/\l)^2^)]/
[\s^2^(Fo^2^)+0.0000+0.0000*P+(0.0163P)^2^+0.0000sin\q/\l]
where P = 0.33333Fo^2^ + 0.66667Fc^2^
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0559
_refine_ls_wR_factor_ref         0.0640
_reflns_number_gt                2498
_reflns_number_total             4935
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            c1sc00083g.txt
_cod_data_source_block           cd201323
_cod_depositor_comments
;
The following automatic conversions were performed:

'_symmetry_cell_setting' value 'Orthorhombic' changed to
'orthorhombic' according to
/usr/data/users/saulius/automatic-downloads/retrospective/RSC/lib/dictionaries/cif_core.dic
dictionary named 'cif_core.dic' version 2.4.2 from 2011-04-26.

Automatic conversion script
Id: cif_fix_values 2281 2013-09-26 08:29:07Z andrius 
;
_cod_original_sg_symbol_H-M      P2(1)2(1)2(1)
_cod_database_code               1515600