Asymmetric tandem conjugate addition−protonation to forge chiral secondary C−O bond for quaternary carbon stereocenters at the nonadjacent β-position
Hong, San-Ni; Liu, Yang; Lee, Richmond; Jiang, Zhiyong; Chem. Commun.  (2017) –; doi:10.1039/C7CC03700G

data_7120270
_publ_section_title
;
 Asymmetric tandem conjugate addition&#x2212;protonation to forge chiral
 secondary C&#x2212;O bond for quaternary carbon stereocenters at the
 nonadjacent \b-position
;
_journal_name_full               'Chem. Commun.'
_journal_paper_doi               10.1039/C7CC03700G
_journal_year                    2017
_chemical_absolute_configuration s
_chemical_formula_moiety         'C29 H26 N2 O6'
_chemical_formula_sum            'C29 H26 N2 O6'
_chemical_formula_weight         498.52
_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
_audit_creation_date             2015-06-10
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_audit_update_record
;
2017-02-09 deposited with the CCDC.
2017-06-13 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 105.597(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.4756(5)
_cell_length_b                   11.9717(6)
_cell_length_c                   17.9467(7)
_cell_measurement_reflns_used    6570
_cell_measurement_temperature    291(2)
_cell_measurement_theta_max      72.0910
_cell_measurement_theta_min      3.8640
_cell_volume                     2581.7(2)
_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, 2008)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      291.15
_diffrn_detector_area_resol_mean 16.2312
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_details
;
  1 omega  -77.00  -52.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000  178.0000 -120.0000 25

  2 omega  -77.00  -50.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000  178.0000    0.0000 27

  3 omega   -4.00   23.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000  -99.0000   60.0000 27

  4 omega -110.00  -85.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      -42.5000  -57.0000  -60.0000 25

  5 omega  -53.00  -21.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      -42.5000  -57.0000  -60.0000 32

  6 omega  -59.00  -24.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      -42.5000  -57.0000    0.0000 35

  7 omega -117.00  -45.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      -42.5000  178.0000  -90.0000 72

  8 omega -115.00  -14.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      -42.5000  -30.0000   61.0000 101

  9 omega  -38.00  -13.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      -42.5000   30.0000 -137.0000 25

 10 omega  -32.00   30.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      -42.5000   30.0000 -120.0000 62

 11 omega  -10.00   71.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       56.0000  -37.0000 -120.0000 81

 12 omega   25.00  103.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       56.0000   78.0000  -51.1004 78

 13 omega   36.00   88.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       56.0000   57.0000   30.0000 52

 14 omega   91.00  117.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       56.0000   57.0000   30.0000 26

 15 omega   82.00  108.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   77.0000  -60.0000 26

 16 omega   90.00  115.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   61.0000    0.0000 25

 17 omega  119.00  176.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   77.0000  -30.0000 57

 18 omega   83.00  109.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   77.0000  -30.0000 26

 19 omega   59.00   91.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   15.0000   60.0000 32

 20 omega   50.00   90.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -30.0000  -90.0000 40

 21 omega   41.00   74.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -45.0000 -180.0000 33

 22 omega   84.00  110.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   30.0000  -90.0000 26

 23 omega   62.00   87.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   15.0000   90.0000 25

 24 omega   90.00  115.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   61.0000  -60.0000 25

 25 omega   90.00  177.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   61.0000   30.0000 87

 26 omega   82.00  171.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   77.0000 -120.0000 89

 27 omega   89.00  117.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   45.0000  -30.0000 28

 28 omega   86.00  113.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   30.0000    0.0000 27

 29 omega   91.00  117.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   61.0000  -90.0000 26

 30 omega   47.00   82.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -30.0000 -120.0000 35

 31 omega   90.00  116.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   61.0000  -30.0000 26

 32 omega   60.00   88.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   15.0000  -30.0000 28

 33 omega   45.00  142.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -77.0000    0.0000 97

 34 omega   85.00  111.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   30.0000   30.0000 26

 35 omega   89.00  115.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   45.0000   30.0000 26

 36 omega  122.00  148.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   77.0000    0.0000 26

 37 omega   89.00  115.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   45.0000    0.0000 26

 38 omega   91.00  117.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   61.0000 -120.0000 26

 39 omega   82.00  108.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   77.0000    0.0000 26

 40 omega  128.00  157.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   77.0000  -90.0000 29

 41 omega   89.00  114.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   45.0000  -60.0000 25

 42 omega   85.00  165.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   30.0000  -30.0000 80

 43 omega   84.00  109.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   30.0000  -60.0000 25

 44 omega   82.00  108.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   77.0000  -90.0000 26

 45 omega   52.00   92.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -94.0000  -60.0000 40

 46 omega   60.00   95.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   15.0000   30.0000 35

 47 omega   41.00   98.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -45.0000   90.0000 57

 48 omega   55.00   88.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -45.0000  -90.0000 33

 49 omega  120.00  157.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   15.0000   90.0000 37

 50 omega   60.00   90.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   15.0000    0.0000 30
;
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0349962000
_diffrn_orient_matrix_UB_12      0.0391017000
_diffrn_orient_matrix_UB_13      0.0717959000
_diffrn_orient_matrix_UB_21      0.1156648000
_diffrn_orient_matrix_UB_22      -0.0319706000
_diffrn_orient_matrix_UB_23      0.0518983000
_diffrn_orient_matrix_UB_31      0.0427574000
_diffrn_orient_matrix_UB_32      0.1184027000
_diffrn_orient_matrix_UB_33      -0.0096967000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0273
_diffrn_reflns_av_unetI/netI     0.0357
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            21898
_diffrn_reflns_point_group_measured_fraction_full 0.951
_diffrn_reflns_point_group_measured_fraction_max 0.951
_diffrn_reflns_theta_full        67.078
_diffrn_reflns_theta_max         67.078
_diffrn_reflns_theta_min         3.678
_diffrn_source                   'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.743
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.94238
_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_density_diffrn    1.283
_exptl_crystal_F_000             1048
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.137
_refine_diff_density_min         -0.166
_refine_diff_density_rms         0.038
_refine_ls_abs_structure_details
;
 Flack x determined using 2952 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.05(9)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.054
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     673
_refine_ls_number_reflns         8788
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.054
_refine_ls_R_factor_all          0.0484
_refine_ls_R_factor_gt           0.0411
_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^)+(0.0520P)^2^+0.0783P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0987
_refine_ls_wR_factor_ref         0.1043
_reflns_Friedel_coverage         0.809
_reflns_Friedel_fraction_full    0.898
_reflns_Friedel_fraction_max     0.898
_reflns_number_gt                7674
_reflns_number_total             8788
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7cc03700g2.cif
_cod_data_source_block           hsn5020
_cod_database_code               7120270
_chemical_oxdiff_formula         C20H20N4O4
_shelx_estimated_absorpt_t_max   0.957
_shelx_estimated_absorpt_t_min   0.866
_reflns_odcompleteness_completeness 99.98
_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:
 C16(H16), C16'(H16')
2.b Secondary CH2 refined with riding coordinates:
 C15(H15A,H15B), C15'(H15C,H15D)
2.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C10(H10), C11(H11), C12(H12), C13(H13),
 C14(H14), C20(H20), C21(H21), C22(H22), C23(H23), C24(H24), C1'(H1'), C2'(H2'),
  C3'(H3'), C4'(H4'), C10'(H10'), C11'(H11'), C12'(H12'), C13'(H13'),
 C14'(H14'), C20'(H20'), C21'(H21'), C22'(H22'), C23'(H23'), C24'(H24')
2.d Idealised Me refined as rotating group:
 C27(H27A,H27B,H27C), C28(H28A,H28B,H28C), C29(H29A,H29B,H29C), C27'(H27D,H27E,
 H27F), C28'(H28D,H28E,H28F), C29'(H29D,H29E,H29F)
;
_shelx_res_checksum              67206
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'