N-Heterocyclic carbene-catalyzed [3+3] cyclocondensation of bromoenals with aldimines: highly enantioselective synthesis of dihydropyridinones
Zhong-Hua Gao; Xiang-Yu Chen; Han-Ming Zhang; Song Ye; Chem.Commun. 51 (2015) 12040–; doi:10.1039/C5cc04593B

data_7117529
_publ_section_title
;
 N-Heterocyclic carbene-catalyzed [3+3] cyclocondensation of bromoenals
 with aldimines: highly enantioselective synthesis of dihydropyridinones
;
_journal_name_full               Chem.Commun.
_journal_page_first              12040
_journal_paper_doi               10.1039/C5cc04593B
_journal_volume                  51
_journal_year                    2015
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C26 H24 Br N O4 S'
_chemical_formula_sum            'C26 H24 Br N O4 S'
_chemical_formula_weight         526.43
_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_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2014-07-15
_audit_creation_method
;
Olex2 1.2
(compiled 2013.12.10 svn.r2850 for OlexSys, GUI svn.r4736)
;
_audit_update_record
;
2015-02-01 deposited with the CCDC.
2015-06-16 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 103.673(3)
_cell_angle_gamma                90
_cell_formula_units_Z            6
_cell_length_a                   17.678(4)
_cell_length_b                   9.8560(19)
_cell_length_c                   20.882(4)
_cell_measurement_reflns_used    9723
_cell_measurement_temperature    173.1500
_cell_measurement_theta_max      27.4694
_cell_measurement_theta_min      1.1854
_cell_volume                     3535.3(13)
_computing_cell_refinement       'CrystalClear (Rigaku Inc., 2007)'
_computing_data_collection       'CrystalClear (Rigaku Inc., 2007)'
_computing_data_reduction        'CrystalClear (Rigaku Inc., 2007)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL (Sheldrick, 2013)'
_computing_structure_solution
;
'SHELXS (Sheldrick, 2013)'
;
_diffrn_ambient_temperature      173.1500
_diffrn_detector_area_resol_mean 28.5714
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device
;
Saturn724 (2x2 bin mode)
;
_diffrn_measurement_device_details
;
AFC10: Fixed Chi 2 circle
;
_diffrn_measurement_device_type  'Saturn724+ CCD'
_diffrn_measurement_method       '\w scans at fixed \c = 45\%'
_diffrn_orient_matrix_type       d*Trek
_diffrn_orient_matrix_UB_11      -0.0244
_diffrn_orient_matrix_UB_12      -0.0526
_diffrn_orient_matrix_UB_13      -0.0048
_diffrn_orient_matrix_UB_21      -0.0741
_diffrn_orient_matrix_UB_22      0.0396
_diffrn_orient_matrix_UB_23      -0.0569
_diffrn_orient_matrix_UB_31      0.0209
_diffrn_orient_matrix_UB_32      -0.0189
_diffrn_orient_matrix_UB_33      -0.0404
_diffrn_radiation_detector       CCD
_diffrn_radiation_monochromator  'Graphite Monochromator'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0527
_diffrn_reflns_av_unetI/netI     0.0783
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            39944
_diffrn_reflns_point_group_measured_fraction_full 0.991
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         27.473
_diffrn_reflns_theta_min         1.004
_diffrn_source                   'Sealed Tube'
_diffrn_source_current           30.0000
_diffrn_source_power             1.5000
_diffrn_source_voltage           50.0000
_exptl_absorpt_coefficient_mu    1.866
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.8226
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'CrystalClear (Rigaku Inc., 2007)'
_exptl_crystal_colour            Colorless
_exptl_crystal_density_diffrn    1.484
_exptl_crystal_description       block
_exptl_crystal_F_000             1620
_exptl_crystal_size_max          0.26
_exptl_crystal_size_mid          0.24
_exptl_crystal_size_min          0.09
_refine_diff_density_max         0.699
_refine_diff_density_min         -0.646
_refine_diff_density_rms         0.069
_refine_ls_abs_structure_details
;
 Flack x determined using 4362 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   0.011(5)
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.113
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     898
_refine_ls_number_reflns         15971
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.113
_refine_ls_R_factor_all          0.0795
_refine_ls_R_factor_gt           0.0616
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0186P)^2^+1.8567P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0964
_refine_ls_wR_factor_ref         0.1038
_reflns_Friedel_coverage         0.869
_reflns_Friedel_fraction_full    0.984
_reflns_Friedel_fraction_max     0.975
_reflns_number_gt                13086
_reflns_number_total             15971
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c5cc04593b2.cif
_cod_data_source_block           sa3517
_cod_original_cell_volume        3535.4(12)
_cod_database_code               7117529
_shelxl_version_number           2013-4
_diffrn_number_total             8561
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C1B(H1B), C1A(H1A), C1(H1)
2.b Secondary CH2 refined with riding coordinates:
 C5B(H5BA,H5BB), C13B(H13A,H13B), C5A(H5AA,H5AB), C13A(H13C,H13D), C5(H5A,H5B),
  C13(H13E,H13F)
2.c Aromatic/amide H refined with riding coordinates:
 C3B(H3B), C8B(H8B), C9B(H9B), C11B(H11B), C15B(H15B), C16B(H16B), C17B(H17B),
 C18B(H18B), C19B(H19B), C21B(H21B), C22B(H22B), C24B(H24B), C25B(H25B),
 C3A(H3A), C8A(H8A), C9A(H9A), C11A(H11A), C15A(H15A), C16A(H16A), C17A(H17A),
 C18A(H18A), C19A(H19A), C21A(H21A), C22A(H22A), C24A(H24A), C25A(H25A), C3(H3),
  C8(H8), C9(H9), C11(H11), C15(H15), C16(H16), C17(H17), C18(H18), C19(H19),
 C21(H21), C22(H22), C24(H24), C25(H25)
2.d Idealised Me refined as rotating group:
 C12B(H12A,H12B,H12C), C26B(H26A,H26B,H26C), C12A(H12D,H12E,H12F), C26A(H26D,
 H26E,H26F), C12(H12G,H12H,H12I), C26(H26G,H26H,H26I)
;
_shelx_res_checksum              54458