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_1546472
_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_absolute_configuration ad
_chemical_formula_moiety         'C31 H35 N O4 S, C H2 Cl2'
_chemical_formula_sum            'C32 H37 Cl2 N O4 S'
_chemical_formula_weight         602.59
_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
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2017-04-12
_audit_creation_method
;
Olex2 1.2
(compiled 2017.02.23 svn.r3390 for OlexSys, GUI svn.r5320)
;
_cell_angle_alpha                90.00
_cell_angle_beta                 109.854(7)
_cell_angle_gamma                90.00
_cell_formula_units_Z            2
_cell_length_a                   9.4913(6)
_cell_length_b                   16.7660(11)
_cell_length_c                   10.7446(7)
_cell_measurement_reflns_used    1586
_cell_measurement_temperature    294.78(10)
_cell_measurement_theta_max      25.5940
_cell_measurement_theta_min      3.8980
_cell_volume                     1608.17(19)
_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      294.78(10)
_diffrn_detector_area_resol_mean 16.0733
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_details
;
  1 omega  -11.00   22.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      -19.5055  -99.0000   60.0000 33

  2 omega   -7.00   20.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      -19.5055  -99.0000 -120.0000 27

  3 omega   46.00   81.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       22.7867  178.0000 -180.0000 35

  4 omega  -35.00   98.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       22.7867   19.0000  -60.0000 133
;
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0204658000
_diffrn_orient_matrix_UB_12      0.0403087000
_diffrn_orient_matrix_UB_13      0.0167825000
_diffrn_orient_matrix_UB_21      -0.0217579000
_diffrn_orient_matrix_UB_22      0.0098378000
_diffrn_orient_matrix_UB_23      -0.0681210000
_diffrn_orient_matrix_UB_31      -0.0736289000
_diffrn_orient_matrix_UB_32      0.0083031000
_diffrn_orient_matrix_UB_33      -0.0009027000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0291
_diffrn_reflns_av_unetI/netI     0.0582
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       7
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            6126
_diffrn_reflns_theta_full        26.02
_diffrn_reflns_theta_max         26.02
_diffrn_reflns_theta_min         3.33
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.302
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.74102
_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    1.244
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             636
_exptl_crystal_size_max          0.29
_exptl_crystal_size_mid          0.27
_exptl_crystal_size_min          0.24
_refine_diff_density_max         0.263
_refine_diff_density_min         -0.274
_refine_diff_density_rms         0.042
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   -0.08(10)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.052
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     387
_refine_ls_number_reflns         4421
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.052
_refine_ls_R_factor_all          0.0690
_refine_ls_R_factor_gt           0.0531
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0600P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1188
_refine_ls_wR_factor_ref         0.1352
_reflns_number_gt                3512
_reflns_number_total             4421
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ol7b01331_si_003.cif
_cod_data_source_block           zhangxz_0411
_cod_original_cell_volume        1608.16(18)
_cod_database_code               1546472
_chemical_oxdiff_formula         'C H N O S'
_reflns_odcompleteness_completeness 99.74
_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, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
2. Others
 Fixed Sof: H32A(0.6) H32B(0.6) H32C(0.4) H32D(0.4) Cl1(0.6) Cl2(0.6)
 Cl1'(0.4) Cl2'(0.4)
3.a Ternary CH refined with riding coordinates:
 C15(H15)
3.b Secondary CH2 refined with riding coordinates:
 C32(H32A,H32B), C32(H32C,H32D)
3.c Aromatic/amide H refined with riding coordinates:
 C1(H1A), C5(H5), C17(H17), C18(H18), C19(H19), C20(H20), C26(H26), C27(H27),
 C29(H29), C30(H30)
3.d X=CH2 refined with riding coordinates:
 C24(H24A,H24B)
3.e Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C12(H12A,H12B,H12C),
 C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C31(H31A,H31B,H31C)
3.f Idealised tetrahedral OH refined as rotating group:
 O1(H1)
;
_olex2_date_sample_data_collection 2017-04-12
_olex2_submission_special_instructions 'No special instructions were received'