Organocatalyzed Michael-Michael Cascade Reaction: Asymmetric Synthesis of Polysubstituted Chromans
Zhen-Xin Jia; Yong-Chun Luo; Xi-Na Cheng; Peng-Fei Xu; Yu-Cheng Gu; Journal of Organic Chemistry 78 (2013) 6488–6494; doi:10.1021/jo400476b

data_4028386
_publ_contact_author_name
;
;
_publ_section_title
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 Organocatalyzed Michael-Michael Cascade Reaction: Asymmetric Synthesis of
 Polysubstituted Chromans
;
_journal_name_full               'Journal of Organic Chemistry'
_journal_page_first              6488
_journal_page_last               6494
_journal_paper_doi               10.1021/jo400476b
_journal_volume                  78
_journal_year                    2013
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C21 H19 Br2 N O6'
_chemical_formula_sum            'C21 H19 Br2 N O6'
_chemical_formula_weight         541.19
_space_group_crystal_system      trigonal
_space_group_IT_number           154
_space_group_name_Hall           'P 32 2"'
_space_group_name_H-M_alt        'P 32 2 1'
_symmetry_space_group_name_Hall  'P 32 2"'
_symmetry_space_group_name_H-M   'P 32 2 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_atom_sites_solution_secondary   difmap
_audit_creation_date             2013-01-09
_audit_creation_method
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  Olex2 1.2
  (compiled Dec  5 2012 16:20:19, GUI svn.r4385)
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_cell_formula_units_Z            6
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_cell_length_b                   18.5929(17)
_cell_length_c                   14.0338(5)
_cell_measurement_reflns_used    3717
_cell_measurement_temperature    292.0(2)
_cell_measurement_theta_max      73.2085
_cell_measurement_theta_min      4.1753
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_computing_cell_refinement
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CrysAlisPro, Agilent Technologies,
Version 1.171.36.20 (release 27-06-2012 CrysAlis171 .NET)
(compiled Jul 11 2012,15:38:31)
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_computing_data_collection
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CrysAlisPro, Agilent Technologies,
Version 1.171.36.20 (release 27-06-2012 CrysAlis171 .NET)
(compiled Jul 11 2012,15:38:31)
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_computing_data_reduction
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CrysAlisPro, Agilent Technologies,
Version 1.171.36.20 (release 27-06-2012 CrysAlis171 .NET)
(compiled Jul 11 2012,15:38:31)
;
_computing_molecular_graphics
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O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_publication_material
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_structure_refinement
;
SHELXL, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_computing_structure_solution    'SUPERFLIP, J. Appl. Cryst. (2007) 40, 786-790'
_diffrn_ambient_temperature      292.0(2)
_diffrn_detector_area_resol_mean 16.0733
_diffrn_measured_fraction_theta_full 0.9671
_diffrn_measured_fraction_theta_max 0.9930
_diffrn_measurement_details
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  1 omega  -16.00   11.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000  -57.0000 -180.0000 27

  2 omega  -69.00  -21.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000  -57.0000 -180.0000 48

  3 omega -124.00  -87.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      -58.0000  -99.0000  -90.0000 37

  4 omega  -50.00   15.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      -58.0000   38.0000 -120.0000 65

  5 omega -126.00  -82.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      -58.0000  -99.0000    0.0000 44

  6 omega   77.00  112.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -       58.0000  160.0000    5.0000 35

  7 omega   93.00  133.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -       58.0000  167.0000  -41.0000 40

  8 omega  107.00  133.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -      116.0000  116.0000   -7.0000 26

  9 omega  102.00  128.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -      116.0000  111.0000   30.0000 26

 10 omega   41.00   66.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -      116.0000  -25.0000  -60.0000 25

 11 omega   61.00   87.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -      116.0000  -38.0000  -90.0000 26

 12 omega  153.00  178.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -      116.0000  111.0000   30.0000 25

 13 omega   53.00   89.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -      116.0000  -25.0000  -30.0000 36

 14 omega   48.00   74.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -      116.0000  -63.0000  150.0000 26

 15 omega   65.00   92.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -      116.0000  -38.0000  -60.0000 27

 16 omega   63.00  114.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -      116.0000 -111.0000 -120.0000 51

 17 omega   63.00   88.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -      116.0000 -111.0000 -150.0000 25

 18 omega  153.00  178.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -      116.0000  116.0000   -7.0000 25

 19 omega   45.00   70.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -      116.0000  -50.0000 -180.0000 25

 20 omega   47.00   80.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -      116.0000 -111.0000  -30.0000 33

 21 omega   93.00  118.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -      116.0000  -63.0000  150.0000 25

 22 omega   44.00   70.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -      116.0000  -38.0000 -150.0000 26

 23 omega   45.00   86.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -      116.0000  -25.0000 -150.0000 41

 24 omega   56.00   89.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -      116.0000  -25.0000 -120.0000 33

 25 omega  134.00  173.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -      116.0000  118.0000   52.0000 39

 26 omega  105.00  138.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -      116.0000  -63.0000  120.0000 33

 27 omega   41.00   85.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -      116.0000  -25.0000  150.0000 44
;
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0589351000
_diffrn_orient_matrix_UB_12      0.0933781000
_diffrn_orient_matrix_UB_13      0.0174195000
_diffrn_orient_matrix_UB_21      0.0737035000
_diffrn_orient_matrix_UB_22      -0.0155019000
_diffrn_orient_matrix_UB_23      0.0087382000
_diffrn_orient_matrix_UB_31      0.0155015000
_diffrn_orient_matrix_UB_32      0.0136687000
_diffrn_orient_matrix_UB_33      -0.1081203000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.5418
_diffrn_reflns_av_R_equivalents  0.0276
_diffrn_reflns_av_unetI/netI     0.0327
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       6
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            14548
_diffrn_reflns_theta_full        73.37
_diffrn_reflns_theta_max         73.37
_diffrn_reflns_theta_min         4.18
_diffrn_source                   'SuperNova (Cu) x-ray Source'
_exptl_absorpt_coefficient_mu    3.927
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.56965
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
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CrysAlisPro, Agilent Technologies,
Version 1.171.36.20 (release 27-06-2012 CrysAlis171 .NET)
(compiled Jul 11 2012,15:38:31)
empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
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_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_density_diffrn    1.283
_exptl_crystal_description       block
_exptl_crystal_F_000             1620
_exptl_crystal_size_max          0.44
_exptl_crystal_size_mid          0.38
_exptl_crystal_size_min          0.36
_platon_squeeze_details
;
;
_refine_diff_density_max         0.203
_refine_diff_density_min         -0.366
_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   0.01(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.938
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     272
_refine_ls_number_reflns         5521
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      0.938
_refine_ls_R_factor_all          0.0488
_refine_ls_R_factor_gt           0.0366
_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^)+(0.0655P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1032
_refine_ls_wR_factor_ref         0.1130
_reflns_number_gt                3999
_reflns_number_total             5521
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            jo400476b_si_002.cif
_cod_data_source_block           jiazhx1228
_cod_original_cell_volume        4201.4(5)
_cod_database_code               4028386
_reflns_odcompleteness_completeness 96.71
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  H4 of C4, H3 of C3, H1 of C1, H6 of C6, {H20A,H20B} of C20, {H18A,H18B} of
  C18, H17 of C17, H16 of C16, H14 of C14, H13 of C13, H7 of C7, H8 of C8,
  {H10A,H10B} of C10
 At 1.5 times of:
  {H21A,H21B,H21C} of C21
2.a Ternary CH refined with riding coordinates:
 C6(H6), C7(H7), C8(H8)
2.b Secondary CH2 refined with riding coordinates:
 C10(H10A,H10B), C18(H18A,H18B), C20(H20A,H20B)
2.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C3(H3), C4(H4), C13(H13), C14(H14), C16(H16), C17(H17)
2.d Idealised Me refined as rotating group:
 C21(H21A,H21B,H21C)
;