Diastereo- and Enantioselective Synthesis of Eight-Membered Heterocycles via an Allylation/Ring Expansion Sequence Enabled by Multiple Catalysis
Yang, Wu-Lin; Wang, Yuan-Lin; Li, Wen; Gu, Bu-Ming; Wang, Si-Wen; Luo, Xiaoyan; Tian, Bo-Xue; Deng, Wei-Ping; ACS Catalysis  (2021) 12557–12564; doi:10.1021/acscatal.1c03711

data_4519057
_publ_section_title
;
 Diastereo- and Enantioselective Synthesis of Eight-Membered Heterocycles
 via an Allylation/Ring Expansion Sequence Enabled by Multiple Catalysis
;
_journal_name_full               'ACS Catalysis'
_journal_page_first              12557
_journal_page_last               12564
_journal_paper_doi               10.1021/acscatal.1c03711
_journal_year                    2021
_chemical_absolute_configuration ad
_chemical_formula_sum            'C25 H26 Br2 N2 O4'
_chemical_formula_weight         578.30
_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'
_atom_sites_solution_hydrogens   mixed
_audit_creation_method           SHELXL-2013
_cell_angle_alpha                90
_cell_angle_beta                 96.451(6)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   23.000(4)
_cell_length_b                   8.9861(17)
_cell_length_c                   25.676(5)
_cell_measurement_reflns_used    6345
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      55.122
_cell_measurement_theta_min      4.919
_cell_volume                     5273.1(17)
_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      293(2)
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_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  0.0740
_diffrn_reflns_av_unetI/netI     0.1355
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       27
_diffrn_reflns_limit_h_min       -27
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            51862
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.498
_diffrn_reflns_theta_min         1.739
_exptl_absorpt_coefficient_mu    3.106
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.5005
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   sadabs
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.457
_exptl_crystal_description       prismatic
_exptl_crystal_F_000             2336
_exptl_crystal_size_max          0.150
_exptl_crystal_size_mid          0.080
_exptl_crystal_size_min          0.050
_refine_diff_density_max         0.562
_refine_diff_density_min         -0.655
_refine_diff_density_rms         0.066
_refine_ls_abs_structure_details
; 
 Flack x determined using 2726 quotients [(I+)-(I-)]/[(I+)+(I-)] 
 (Parsons and Flack (2004), Acta Cryst. A60, s61). 
;
_refine_ls_abs_structure_Flack   0.030(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.019
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1247
_refine_ls_number_reflns         19500
_refine_ls_number_restraints     186
_refine_ls_restrained_S_all      1.022
_refine_ls_R_factor_all          0.1914
_refine_ls_R_factor_gt           0.0722
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0229P)^2^+12.0296P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1420
_refine_ls_wR_factor_ref         0.1889
_reflns_Friedel_coverage         0.867
_reflns_Friedel_fraction_full    0.994
_reflns_Friedel_fraction_max     0.994
_reflns_number_gt                8337
_reflns_number_total             19500
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs1c03711_si_004.cif
_cod_data_source_block           mo_d8v21499_0m
_cod_original_cell_volume        5273.3(18)
_cod_original_sg_symbol_H-M      'P 21'
_cod_database_code               4519057
_shelx_estimated_absorpt_t_min   0.653
_shelx_estimated_absorpt_t_max   0.860
_shelxl_version_number           2013-4
_shelx_res_checksum              94343
_shelx_hkl_checksum              36803