Enantioselective Synthesis of Functionalized 4-Aryl Hydrocoumarins and 4-Aryl Hydroquinolin-2-ones via Intramolecular Vinylogous Rauhut-Currier Reaction of para-Quinone Methides.
Zhang, Xiang-Zhi; Gan, Kang-Ji; Liu, Xiao-Xue; Deng, Yu-Hua; Wang, Fang-Xin; Yu, Ke-Yin; Zhang, Jing; Fan, Chun-An; Organic letters 19 (2017) 3207–3210; doi:10.1021/acs.orglett.7b01331

data_1546473
_publ_section_title
;
 Enantioselective Synthesis of Functionalized 4-Aryl Hydrocoumarins and
 4-Aryl Hydroquinolin-2-ones via Intramolecular Vinylogous Rauhut-Currier
 Reaction of para-Quinone Methides.
;
_journal_issue                   12
_journal_name_full               'Organic letters'
_journal_page_first              3207
_journal_page_last               3210
_journal_paper_doi               10.1021/acs.orglett.7b01331
_journal_volume                  19
_journal_year                    2017
_chemical_formula_moiety         'C24 H27 Br O3'
_chemical_formula_sum            'C24 H27 Br O3'
_chemical_formula_weight         443.36
_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     direct
_audit_creation_date             2016-12-21
_audit_creation_method
;
Olex2 1.2
(compiled 2016.11.30 svn.r3356 for OlexSys, GUI svn.r5269)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.1261(4)
_cell_length_b                   11.2710(7)
_cell_length_c                   19.4856(11)
_cell_measurement_reflns_used    908
_cell_measurement_temperature    254(9)
_cell_measurement_theta_max      21.4130
_cell_measurement_theta_min      4.1360
_cell_volume                     2223.9(2)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      254(9)
_diffrn_detector_area_resol_mean 16.0733
_diffrn_measured_fraction_theta_full 0.9958
_diffrn_measured_fraction_theta_max 0.7537
_diffrn_measurement_details
;
  1 omega   59.00   91.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -       22.7867   77.0000  -60.0000 32

  2 omega    3.00   64.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -       22.7867   77.0000 -180.0000 61

  3 omega    4.00   55.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -       22.7867   77.0000   90.0000 51
;
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0220267000
_diffrn_orient_matrix_UB_12      -0.0592479000
_diffrn_orient_matrix_UB_13      -0.0044565000
_diffrn_orient_matrix_UB_21      -0.0227992000
_diffrn_orient_matrix_UB_22      0.0144023000
_diffrn_orient_matrix_UB_23      -0.0334184000
_diffrn_orient_matrix_UB_31      0.0624391000
_diffrn_orient_matrix_UB_32      -0.0155695000
_diffrn_orient_matrix_UB_33      -0.0137565000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.7107
_diffrn_reflns_av_R_equivalents  0.0364
_diffrn_reflns_av_unetI/netI     0.0809
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       5
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            5452
_diffrn_reflns_point_group_measured_fraction_full 0.872
_diffrn_reflns_point_group_measured_fraction_max 0.869
_diffrn_reflns_theta_full        25.500
_diffrn_reflns_theta_max         26.011
_diffrn_reflns_theta_min         3.419
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.869
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.51882
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.324
_exptl_crystal_description       block
_exptl_crystal_F_000             920
_exptl_crystal_size_max          0.21
_exptl_crystal_size_mid          0.17
_exptl_crystal_size_min          0.14
_refine_diff_density_max         0.523
_refine_diff_density_min         -0.614
_refine_diff_density_rms         0.062
_refine_ls_abs_structure_details
;
 Flack x determined using 536 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.009(14)
_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     260
_refine_ls_number_reflns         3810
_refine_ls_number_restraints     60
_refine_ls_restrained_S_all      1.077
_refine_ls_R_factor_all          0.1243
_refine_ls_R_factor_gt           0.0661
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0370P)^2^+2.0967P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1194
_refine_ls_wR_factor_ref         0.1500
_reflns_Friedel_coverage         0.531
_reflns_Friedel_fraction_full    0.706
_reflns_Friedel_fraction_max     0.700
_reflns_number_gt                2280
_reflns_number_total             3810
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ol7b01331_si_002.cif
_cod_data_source_block           zhaoxh_1219
_cod_database_code               1546473
_chemical_oxdiff_formula         'C H S N'
_reflns_odcompleteness_completeness 99.58
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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, All O(H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(O2) \\sim Ueq, Uanis(C9) \\sim Ueq, Uanis(O3) \\sim Ueq, Uanis(C10) \\sim
Ueq, Uanis(C11) \\sim Ueq, Uanis(C12) \\sim Ueq, Uanis(C13) \\sim Ueq,
Uanis(C14) \\sim Ueq, Uanis(C15) \\sim Ueq, Uanis(Br1) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
3.a Ternary CH refined with riding coordinates:
 C7(H7)
3.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C5(H5), C11(H11), C12(H12), C14(H14)
3.c X=CH2 refined with riding coordinates:
 C24(H24A,H24B)
3.d Idealised Me refined as rotating group:
 C17(H17A,H17B,H17C), C18(H18A,H18B,H18C), C19(H19A,H19B,H19C), C21(H21A,H21B,
 H21C), C22(H22A,H22B,H22C), C23(H23A,H23B,H23C)
3.e Idealised tetrahedral OH refined as rotating group:
 O0AA(H0AA)
;
_shelx_shelxl_version_number     2014/7
_olex2_date_sample_data_collection 2016-12-19
_olex2_submission_special_instructions 'No special instructions were received'