Phosphine-catalyzed asymmetric [4+1] annulation of activated alpha,beta-unsaturated ketones with Morita-Baylis-Hillman carbonates: enantioselective synthesis of spirooxindoles containing two adjacent quaternary stereocenters
Fang-Le Hu; Yin Wei; Min Shi; Chem.Commun. 50 (2014) 8912–; doi:10.1039/C4cc03479A

data_7115391
_publ_section_title
;
 Phosphine-catalyzed asymmetric [4+1] annulation of activated
 alpha,beta-unsaturated ketones with Morita-Baylis-Hillman carbonates:
 enantioselective synthesis of spirooxindoles containing two adjacent
 quaternary stereocenters
;
_journal_name_full               Chem.Commun.
_journal_page_first              8912
_journal_paper_doi               10.1039/C4cc03479A
_journal_volume                  50
_journal_year                    2014
_chemical_absolute_configuration ad
_chemical_formula_sum            'C30 H22 Br Cl2 N3 O6'
_chemical_formula_weight         671.31
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_audit_creation_method           SHELXL-2013
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   13.3390(14)
_cell_length_b                   15.3601(16)
_cell_length_c                   30.918(3)
_cell_measurement_reflns_used    4040
_cell_measurement_temperature    140(2)
_cell_measurement_theta_max      19.94
_cell_measurement_theta_min      2.41
_cell_volume                     6334.7(11)
_computing_cell_refinement       'Bruker SAINT'
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'Bruker SAINT'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'
_computing_structure_refinement  'SHELXL-2013 (Sheldrick, 2013)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_diffrn_ambient_temperature      140(2)
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0936
_diffrn_reflns_av_unetI/netI     0.1104
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -38
_diffrn_reflns_number            46221
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.998
_diffrn_reflns_theta_min         1.317
_exptl_absorpt_coefficient_mu    1.511
_exptl_absorpt_correction_T_max  0.7461
_exptl_absorpt_correction_T_min  0.6004
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   sadabs
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.408
_exptl_crystal_F_000             2720
_exptl_crystal_size_max          0.280
_exptl_crystal_size_mid          0.120
_exptl_crystal_size_min          0.050
_platon_squeeze_details
;
;
_refine_diff_density_max         0.585
_refine_diff_density_min         -0.777
_refine_diff_density_rms         0.142
_refine_ls_abs_structure_details
; 
 Flack x determined using 2928 quotients [(I+)-(I-)]/[(I+)+(I-)] 
 (Parsons and Flack (2004), Acta Cryst. A60, s61). 
;
_refine_ls_abs_structure_Flack   0.097(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.042
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     757
_refine_ls_number_reflns         12441
_refine_ls_number_restraints     21
_refine_ls_restrained_S_all      1.044
_refine_ls_R_factor_all          0.1212
_refine_ls_R_factor_gt           0.0929
_refine_ls_shift/su_max          0.011
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1061P)^2^+31.4436P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2276
_refine_ls_wR_factor_ref         0.2416
_reflns_Friedel_coverage         0.815
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     1.000
_reflns_number_gt                8764
_reflns_number_total             12441
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c4cc03479a2.cif
_cod_data_source_block           mo_dm14108_0m
_cod_database_code               7115391
_shelx_estimated_absorpt_t_min   0.677
_shelx_estimated_absorpt_t_max   0.928
_shelxl_version_number           2013-4
_shelx_res_checksum              64081