Asymmetric synthesis of bicyclic dihydropyrans via organocatalytic inverse-electron-demand oxo-Diels-Alder reactions of enolizable aliphatic aldehydes.
Li, Jun-Long; Yang, Kai-Chuan; Li, Yi; Li, Qiang; Zhu, Hong-Ping; Han, Bo; Peng, Cheng; Zhi, Yong-Gang; Gou, Xiao-Jun; Chemical communications (Cambridge, England) 52 (2016) 10617–10620; doi:10.1039/c6cc05001h

data_7124846
_publ_section_title
;
 Asymmetric synthesis of bicyclic dihydropyrans via organocatalytic
 inverse-electron-demand oxo-Diels-Alder reactions of enolizable aliphatic
 aldehydes.
;
_journal_issue                   70
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              10617
_journal_page_last               10620
_journal_paper_doi               10.1039/c6cc05001h
_journal_volume                  52
_journal_year                    2016
_chemical_absolute_configuration rmad
_chemical_formula_moiety         '2(C21 H20 Br N O3)'
_chemical_formula_sum            'C42 H40 Br2 N2 O6'
_chemical_formula_weight         828.58
_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'
_atom_sites_solution_hydrogens   geom
_audit_block_doi                 10.5517/ccdc.csd.cc1lpy7g
_audit_creation_date             2015-10-21
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_audit_update_record
;
2016-05-19 deposited with the CCDC.
2016-07-13 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 111.095(5)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   9.5936(4)
_cell_length_b                   17.0134(7)
_cell_length_c                   12.4020(5)
_cell_measurement_reflns_used    6253
_cell_measurement_temperature    292.71(10)
_cell_measurement_theta_max      72.0090
_cell_measurement_theta_min      4.6140
_cell_volume                     1888.60(15)
_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      292.71(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 15.9595
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_details
;
  1 omega   20.00  104.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.5421   57.0000 -180.0000 84

  2 omega   23.00   90.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.5421 -125.0000 -120.0000 67

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

  4 omega  -31.00   53.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.5421  -57.0000 -150.0000 84

  5 omega    1.00   75.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.5421  -99.0000  -30.0000 74

  6 omega    7.00  108.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.5421   19.0000  -90.0000 101

  7 omega    1.00   75.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.5421  -99.0000   30.0000 74

  8 omega    7.00  108.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.5421   19.0000 -180.0000 101

  9 omega   18.00  106.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.5421   38.0000  -90.0000 88

 10 omega  -33.00   55.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.5421  -38.0000 -120.0000 88

 11 omega   18.00  106.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.5421   38.0000   60.0000 88

 12 omega   81.00  176.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000  120.0000 95

 13 omega   87.00  178.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   30.0000 -150.0000 91

 14 omega   90.00  175.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   61.0000 -180.0000 85

 15 omega   38.00  116.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000 -111.0000  -30.0000 78

 16 omega   38.00   91.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000 -180.0000 53

 17 omega   87.00  178.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   30.0000 -120.0000 91

 18 omega   38.00  116.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000 -111.0000  -90.0000 78

 19 omega   87.00  178.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   30.0000 -180.0000 91

 20 omega  124.00  172.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000 -180.0000 48

 21 omega   70.00   95.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -45.0000  120.0000 25

 22 omega   87.00  113.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   30.0000  150.0000 26

 23 omega   81.00  107.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000 -180.0000 26

 24 omega   93.00  118.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   45.0000  150.0000 25

 25 omega   98.00  125.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   45.0000 -180.0000 27

 26 omega  130.00  172.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  111.0000  -60.0000 42

 27 omega   90.00  116.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   61.0000 -150.0000 26

 28 omega   90.00  116.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   61.0000  150.0000 26

 29 omega   82.00  107.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000   90.0000 25

 30 omega   43.00   70.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000 -150.0000 27

 31 omega   43.00   70.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -61.0000   30.0000 27

 32 omega  142.00  171.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000 -150.0000 29

 33 omega  127.00  175.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000  150.0000 48

 34 omega   92.00  119.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   45.0000 -150.0000 27

 35 omega   91.00  123.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -61.0000   30.0000 32

 36 omega   90.00  117.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   61.0000  120.0000 27

 37 omega   81.00  108.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000 -150.0000 27

 38 omega  120.00  176.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000   90.0000 56

 39 omega   81.00  108.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000  150.0000 27

 40 omega   90.00  169.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   61.0000    0.0000 79

 41 omega   78.00  105.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   15.0000  150.0000 27
;
_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      0.1244161000
_diffrn_orient_matrix_UB_12      -0.0511053000
_diffrn_orient_matrix_UB_13      0.0840562000
_diffrn_orient_matrix_UB_21      0.0820083000
_diffrn_orient_matrix_UB_22      -0.0007593000
_diffrn_orient_matrix_UB_23      -0.0863407000
_diffrn_orient_matrix_UB_31      0.0861501000
_diffrn_orient_matrix_UB_32      0.0747646000
_diffrn_orient_matrix_UB_33      0.0565877000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0568
_diffrn_reflns_av_unetI/netI     0.0594
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            20048
_diffrn_reflns_point_group_measured_fraction_full 0.969
_diffrn_reflns_point_group_measured_fraction_max 0.969
_diffrn_reflns_theta_full        67.072
_diffrn_reflns_theta_max         67.072
_diffrn_reflns_theta_min         4.622
_diffrn_source                   'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.132
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.08207
_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    1.457
_exptl_crystal_F_000             848
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.829
_refine_diff_density_min         -0.518
_refine_diff_density_rms         0.088
_refine_ls_abs_structure_details
;
 Flack x determined using 2254 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.030(15)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.014
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     473
_refine_ls_number_reflns         6542
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.014
_refine_ls_R_factor_all          0.0616
_refine_ls_R_factor_gt           0.0546
_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^)+(0.0935P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1360
_refine_ls_wR_factor_ref         0.1437
_reflns_Friedel_coverage         0.870
_reflns_Friedel_fraction_full    0.937
_reflns_Friedel_fraction_max     0.937
_reflns_number_gt                5825
_reflns_number_total             6542
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c6cc05001h2.cif
_cod_data_source_block           yxq-ljl-ykc-151014b
_cod_original_cell_volume        1888.61(14)
_cod_database_code               7124846
_reflns_odcompleteness_completeness 99.94
_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:
 C00E(H00I), C00F(H00J), C00P(H00P), C00R(H00T), C00X(H00X), C010(H010)
2.b Secondary CH2 refined with riding coordinates:
 C00G(H00L,H00M), C00N(H00A,H00C), C00Q(H00R,H00S), C00Y(H00G,H00H)
2.c Aromatic/amide H refined with riding coordinates:
 C00B(H00B), C00I(H00N), C00K(H00K), C00L(H00O), C00M(H00Q), C00Z(H00Z),
 C011(H011), C013(H013), C014(H014), C017(H017), C019(H019), C01A(H01E),
 C01B(H01H), C01C(H01C), C01D(H01I), C01E(H01J), C01F(H01F), C01G(H01G)
2.d Idealised Me refined as rotating group:
 C00U(H00D,H00E,H00F), C016(H01A,H01B,H01D)
2.e Idealised tetrahedral OH refined as rotating group:
 O006(H006), O008(H008)
;
_shelx_res_checksum              48764
_shelx_shelxl_version_number     2014/7
_olex2_date_sample_data_collection 2015-10-21
_olex2_submission_special_instructions 'No special instructions were received'