Catalytic enantioselective cross-dehydrogenative coupling of 3,6-dihydro-2H-pyrans with aldehydes
Xin, Xiaodong; Pan, Xinhui; Meng, Zhilin; Liu, Xigong; Liu, Lei; Organic Chemistry Frontiers 6 (2019) 1448–; doi:10.1039/C9QO00123A

data_1554738
_publ_section_title
;
 Catalytic enantioselective cross-dehydrogenative coupling of
 3,6-dihydro-2H-pyrans with aldehydes
;
_journal_issue                   9
_journal_name_full               'Organic Chemistry Frontiers'
_journal_page_first              1448
_journal_paper_doi               10.1039/C9QO00123A
_journal_volume                  6
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C24 H27 Br O3'
_chemical_formula_sum            'C24 H27 Br O3'
_chemical_formula_weight         443.37
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2016-06-08
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_audit_update_record
;
2019-01-19 deposited with the CCDC.	2019-03-08 downloaded from the CCDC.
;
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   5.4590(3)
_cell_length_b                   7.8884(3)
_cell_length_c                   51.7461(18)
_cell_measurement_reflns_used    3860
_cell_measurement_temperature    295(2)
_cell_measurement_theta_max      69.4260
_cell_measurement_theta_min      5.1110
_cell_volume                     2228.33(17)
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      295.15
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.0355
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_details
;
  1 omega   -4.00   44.00   0.3000    1.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000  -99.0000    0.0000 160

  2 omega  -82.00  -32.80   0.3000    1.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000  178.0000  -30.0000 164

  3 omega -129.00  -81.00   0.3000    2.5000
omega____ theta____ kappa____ phi______ frames
    -      -55.6874  -94.0000   90.0000 160

  4 omega  -81.00   13.50   0.3000    2.5000
omega____ theta____ kappa____ phi______ frames
    -      -55.6874   61.0000  -90.0000 315

  5 omega -128.00   20.50   0.3000    2.5000
omega____ theta____ kappa____ phi______ frames
    -      -55.6874   15.0000 -150.0000 495

  6 omega -125.00  -32.00   0.3000    2.5000
omega____ theta____ kappa____ phi______ frames
    -      -55.6874  -61.0000 -150.0000 310

  7 omega   38.00  113.90   0.3000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      111.3749 -111.0000  150.0000 253

  8 omega   39.00  103.20   0.3000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      111.3749  -50.0000  -30.0000 214

  9 omega   36.00   93.00   0.3000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      111.3749  -25.0000 -120.0000 190

 10 omega  100.00  178.00   0.3000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      111.3749  111.0000  -30.0000 260

 11 omega   38.00   92.00   0.3000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      111.3749  -37.0000  -90.0000 180

 12 omega   39.00  103.20   0.3000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      111.3749  -50.0000 -120.0000 214

 13 omega   38.00   92.00   0.3000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      111.3749  -37.0000   30.0000 180

 14 omega   38.00  152.00   0.3000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      111.3749  -91.0000   60.0000 380

 15 omega  -33.00   72.00   0.3000    1.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000   77.0000  -90.0000 350

 16 omega   18.00  115.50   0.3000    2.5000
omega____ theta____ kappa____ phi______ frames
    -       55.6874 -125.0000   30.0000 325

 17 omega   31.00  124.00   0.3000    2.5000
omega____ theta____ kappa____ phi______ frames
    -       55.6874   61.0000   30.0000 310

 18 omega   23.00  128.00   0.3000    2.5000
omega____ theta____ kappa____ phi______ frames
    -       55.6874   77.0000  -60.0000 350

 19 omega   31.00  124.00   0.3000    2.5000
omega____ theta____ kappa____ phi______ frames
    -       55.6874   61.0000  120.0000 310

 20 omega   67.00  178.00   0.3000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      111.3749   25.0000  -60.0000 370

 21 omega   67.00  178.00   0.3000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      111.3749   25.0000   60.0000 370

 22 omega   79.00  116.20   0.3000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      111.3749   37.0000  120.0000 124

 23 omega   38.00  113.90   0.3000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      111.3749 -111.0000  -90.0000 253

 24 omega   67.00  178.00   0.3000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      111.3749   25.0000 -150.0000 370
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0363419000
_diffrn_orient_matrix_UB_12      0.1842637000
_diffrn_orient_matrix_UB_13      -0.0091223000
_diffrn_orient_matrix_UB_21      -0.2727897000
_diffrn_orient_matrix_UB_22      0.0099231000
_diffrn_orient_matrix_UB_23      -0.0074948000
_diffrn_orient_matrix_UB_31      -0.0625800000
_diffrn_orient_matrix_UB_32      0.0641647000
_diffrn_orient_matrix_UB_33      0.0273169000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0420
_diffrn_reflns_av_unetI/netI     0.0245
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       61
_diffrn_reflns_limit_l_min       -50
_diffrn_reflns_number            15055
_diffrn_reflns_theta_full        66.53
_diffrn_reflns_theta_max         66.53
_diffrn_reflns_theta_min         3.42
_diffrn_source                   'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.672
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.30782
_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_density_diffrn    1.322
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             920
_exptl_crystal_size_max          0.46
_exptl_crystal_size_mid          0.24
_exptl_crystal_size_min          0.14
_refine_diff_density_max         0.579
_refine_diff_density_min         -0.602
_refine_diff_density_rms         0.068
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.03(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.055
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     255
_refine_ls_number_reflns         3945
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.055
_refine_ls_R_factor_all          0.0752
_refine_ls_R_factor_gt           0.0680
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0996P)^2^+1.4057P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1962
_refine_ls_wR_factor_ref         0.2027
_reflns_number_gt                3299
_reflns_number_total             3945
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            c9qo00123a2.cif
_cod_data_source_block           160607_sd_1
_cod_original_cell_volume        2228.33(16)
_cod_database_code               1554738
_chemical_oxdiff_formula         'C H N O Br'
_reflns_odcompleteness_completeness 99.84
_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
2.a Ternary CH refined with riding coordinates:
 C9(H9), C13(H13)
2.b Secondary CH2 refined with riding coordinates:
 C17(H17A,H17B), C8(H8A,H8B), C16(H16A,H16B), C10(H10A,H10B), C11(H11A,H11B)
2.c Aromatic/amide H refined with riding coordinates:
 C14(H14), C22(H22), C5(H5), C23(H23), C20(H20), C3(H3), C19(H19), C2(H2),
 C6(H6)
2.d Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), C24(H24A,H24B,H24C)
;
_olex2_submission_special_instructions 'No special instructions were received'