Asymmetric synthesis of dihydrocoumarins via organocatalytic hetero-Diels-Alder reaction of ortho-quinone methides
Li, Wenjun; Zhang, Lili; Liu, Yang; Liu, Kun; Liu, Zhantao; He, Ningning; Org. Biomol. Chem.  (2017) –; doi:10.1039/C7OB02325A

data_7155905
_publ_section_title
;
 Asymmetric synthesis of dihydrocoumarins via organocatalytic
 hetero-Diels-Alder reaction of ortho-quinone methides
;
_journal_name_full               'Org. Biomol. Chem.'
_journal_paper_doi               10.1039/C7OB02325A
_journal_year                    2017
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C32 H36 Br N O4'
_chemical_formula_sum            'C32 H36 Br N O4'
_chemical_formula_weight         578.53
_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
_atom_sites_solution_primary     dual
_audit_creation_date             2017-07-06
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5337)
;
_audit_update_record
;
2017-07-06 deposited with the CCDC.
2017-09-28 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.3304(5)
_cell_length_b                   11.1679(5)
_cell_length_c                   24.5971(12)
_cell_measurement_reflns_used    9141
_cell_measurement_temperature    150
_cell_measurement_theta_max      26.349
_cell_measurement_theta_min      2.463
_cell_volume                     2837.7(2)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      150.0
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_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  0.0487
_diffrn_reflns_av_unetI/netI     0.0234
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            57777
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.432
_diffrn_reflns_theta_min         2.463
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.486
_exptl_absorpt_correction_T_max  0.4908
_exptl_absorpt_correction_T_min  0.4109
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2014/5 (Bruker,2014/5) was used for absorption correction. wR2(int) was 0.1043 before and 0.0587 after correction. The Ratio of minimum to maximum transmission is 0.8372. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.354
_exptl_crystal_description       block
_exptl_crystal_F_000             1208
_exptl_crystal_size_max          0.42
_exptl_crystal_size_mid          0.38
_exptl_crystal_size_min          0.31
_refine_diff_density_max         0.775
_refine_diff_density_min         -0.732
_refine_diff_density_rms         0.059
_refine_ls_abs_structure_details
;
 Flack x determined using 2165 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.127(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.038
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     351
_refine_ls_number_reflns         5823
_refine_ls_number_restraints     8
_refine_ls_restrained_S_all      1.040
_refine_ls_R_factor_all          0.0396
_refine_ls_R_factor_gt           0.0337
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0412P)^2^+2.2168P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0815
_refine_ls_wR_factor_ref         0.0848
_reflns_Friedel_coverage         0.770
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     1.000
_reflns_number_gt                5341
_reflns_number_total             5823
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7ob02325a2.cif
_cod_data_source_block           cxy0061
_cod_database_code               7155905
_shelx_shelxl_version_number     2016/6
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
2. Restrained distances
 H1-H30A
 2.1 with sigma of 0.04
 H1-H26C
 2.1 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
C2 \\sim C3: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
4.a Ternary CH refined with riding coordinates:
 C12(H12)
4.b Secondary CH2 refined with riding coordinates:
 C10(H10A,H10B)
4.c Aromatic/amide H refined with riding coordinates:
 N1(H1A), C3(H3), C4(H4), C5(H5), C6(H6), C14(H14), C15(H15), C16(H16),
 C17(H17), C20(H20), C24(H24)
4.d Idealised Me refined as rotating group:
 C11(H11A,H11B,H11C), C26(H26A,H26B,H26C), C27(H27A,H27B,H27C), C28(H28A,H28B,
 H28C), C30(H30A,H30B,H30C), C31(H31A,H31B,H31C), C32(H32A,H32B,H32C)
4.e Idealised tetrahedral OH refined as rotating group:
 O1(H1)
;
_shelx_res_checksum              70094
_olex2_submission_special_instructions 'No special instructions were received'