Asymmetric synthesis of chromans via the Friedel–Crafts alkylation–hemiketalization catalysed by an N,N′-dioxide scandium(iii) complex
Hao, Xiaoyu; Lin, Lili; Tan, Fei; Ge, Shulin; Liu, Xiaohua; Feng, Xiaoming; Organic Chemistry Frontiers 4 (2017) 1647–; doi:10.1039/C7QO00323D

data_1553795
_publ_section_title
;
 Asymmetric synthesis of chromans via the Friedel--Crafts
 alkylation--hemiketalization catalysed by an N,N&#x2032;-dioxide
 scandium(iii) complex
;
_journal_issue                   8
_journal_name_full               'Organic Chemistry Frontiers'
_journal_page_first              1647
_journal_paper_doi               10.1039/C7QO00323D
_journal_volume                  4
_journal_year                    2017
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C19 H19 Br O6'
_chemical_formula_sum            'C19 H19 Br O6'
_chemical_formula_weight         423.25
_space_group_crystal_system      orthorhombic
_space_group_IT_number           18
_space_group_name_Hall           'P 2 2ab'
_space_group_name_H-M_alt        'P 21 21 2'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2016-12-23
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5269)
;
_audit_update_record
;
2016-12-26 deposited with the CCDC.
2017-05-19 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   22.0623(4)
_cell_length_b                   14.5144(3)
_cell_length_c                   5.67392(10)
_cell_measurement_reflns_used    6046
_cell_measurement_temperature    294.08(10)
_cell_measurement_theta_max      72.2670
_cell_measurement_theta_min      5.0440
_cell_volume                     1816.91(6)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_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_environment      air
_diffrn_ambient_temperature      294.08(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 15.9595
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_details
;
  1 omega  -30.00   56.00   1.0000    1.6500
omega____ theta____ kappa____ phi______ frames
    -       36.5421  -64.0000  158.0000 86

  2 omega    1.00   75.00   1.0000    1.6500
omega____ theta____ kappa____ phi______ frames
    -       36.5421  -99.0000   90.0000 74

  3 omega    1.00   75.00   1.0000    1.6500
omega____ theta____ kappa____ phi______ frames
    -       36.5421  -99.0000 -180.0000 74

  4 omega   20.00  104.00   1.0000    1.6500
omega____ theta____ kappa____ phi______ frames
    -       36.5421   57.0000  150.0000 84

  5 omega    0.00   26.00   1.0000    1.6500
omega____ theta____ kappa____ phi______ frames
    -       36.5421   94.0000  120.4310 26

  6 omega   40.00   98.00   1.0000    6.6200
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -45.0000  120.0000 58

  7 omega   91.00  176.00   1.0000    6.6200
omega____ theta____ kappa____ phi______ frames
    -      108.0000   45.0000 -150.0000 85

  8 omega   57.00  150.00   1.0000    6.6200
omega____ theta____ kappa____ phi______ frames
    -      108.0000  178.0000   30.0000 93

  9 omega   37.00  146.00   1.0000    6.6200
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -15.0000  -30.0000 109

 10 omega   40.00   98.00   1.0000    6.6200
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -45.0000 -180.0000 58

 11 omega  100.00  178.00   1.0000    6.6200
omega____ theta____ kappa____ phi______ frames
    -      108.0000  111.0000 -120.0000 78

 12 omega   41.00  113.00   1.0000    6.6200
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -55.0000  -27.0000 72

 13 omega   20.00  104.00   1.0000    1.6500
omega____ theta____ kappa____ phi______ frames
    -       36.5421   57.0000   60.0000 84

 14 omega  -31.00   63.00   1.0000    1.6500
omega____ theta____ kappa____ phi______ frames
    -       36.5421  -77.0000  -60.0000 94

 15 omega   18.00  106.00   1.0000    1.6500
omega____ theta____ kappa____ phi______ frames
    -       36.5421   38.0000 -120.0000 88

 16 omega   17.00  103.00   1.0000    1.6500
omega____ theta____ kappa____ phi______ frames
    -       36.5421   64.0000  -65.0000 86
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'New Gemini, Dual, Cu at zero, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0494497000
_diffrn_orient_matrix_UB_12      -0.0512997000
_diffrn_orient_matrix_UB_13      0.1400786000
_diffrn_orient_matrix_UB_21      0.0492838000
_diffrn_orient_matrix_UB_22      -0.0486828000
_diffrn_orient_matrix_UB_23      0.1464371000
_diffrn_orient_matrix_UB_31      -0.0016508000
_diffrn_orient_matrix_UB_32      0.0791130000
_diffrn_orient_matrix_UB_33      0.1807623000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0440
_diffrn_reflns_av_unetI/netI     0.0374
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       6
_diffrn_reflns_limit_l_min       -4
_diffrn_reflns_number            10039
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        67.078
_diffrn_reflns_theta_max         67.078
_diffrn_reflns_theta_min         5.036
_diffrn_source                   'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.378
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.29296
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
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    1.547
_exptl_crystal_F_000             864
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.35
_exptl_crystal_size_min          0.25
_refine_diff_density_max         0.579
_refine_diff_density_min         -0.633
_refine_diff_density_rms         0.098
_refine_ls_abs_structure_details
;
 Flack x determined using 1279 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.011(11)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.071
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     239
_refine_ls_number_reflns         3260
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.071
_refine_ls_R_factor_all          0.0429
_refine_ls_R_factor_gt           0.0420
_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^)+(0.0768P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1027
_refine_ls_wR_factor_ref         0.1042
_reflns_Friedel_coverage         0.702
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     1.000
_reflns_number_gt                3171
_reflns_number_total             3260
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7qo00323d2.cif
_cod_data_source_block           fxm-ldf-4
_cod_database_code               1553795
_reflns_odcompleteness_completeness 99.79
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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.a Ternary CH refined with riding coordinates:
 C00H(H00H)
2.b Secondary CH2 refined with riding coordinates:
 C00M(H00F,H00G)
2.c Aromatic/amide H refined with riding coordinates:
 C008(H008), C00C(H00C), C00D(H00D), C00I(H00I), C00J(H00J), C00O(H00O)
2.d Idealised Me refined as rotating group:
 C00L(H00A,H00B,H00E), C00P(H00K,H00L,H00M), C00Q(H00N,H00P,H00Q)
2.e Idealised tetrahedral OH refined as rotating group:
 O005(H005)
;
_shelx_shelxl_version_number     2014/7
_olex2_date_sample_data_collection 2016-12-23
_olex2_submission_special_instructions 'No special instructions were received'