Asymmetric domino 1,6-addition/annulation reaction of 3-cyano-4-alkenyl-2H-chromen-2-ones with isatin-derived MBH carbonates: enantioselective synthesis of 3,3′-cyclopentenylspirooxindoles bearing 2H-chromen-2-ones
Wang, Zhen-Hua; Lei, Chuan-Wen; Zhang, Xia-Yan; You, Yong; Zhao, Jian-Qiang; Yuan, Wei-Cheng; Organic Chemistry Frontiers 6 (2019) 3342–; doi:10.1039/C9QO00890J

data_1555113
_publ_section_title
;
 Asymmetric domino 1,6-addition/annulation reaction of
 3-cyano-4-alkenyl-2H-chromen-2-ones with isatin-derived MBH carbonates:
 enantioselective synthesis of 3,3&#x2032;-cyclopentenylspirooxindoles
 bearing 2H-chromen-2-ones
;
_journal_issue                   19
_journal_name_full               'Organic Chemistry Frontiers'
_journal_page_first              3342
_journal_paper_doi               10.1039/C9QO00890J
_journal_volume                  6
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C33 H25 Cl N2 O5'
_chemical_formula_sum            'C33 H25 Cl N2 O5'
_chemical_formula_weight         565.00
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_space_group_name_Hall           'P 1'
_space_group_name_H-M_alt        'P 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2018-11-06
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2018-11-06 deposited with the CCDC.	2019-08-14 downloaded from the CCDC.
;
_cell_angle_alpha                69.855(4)
_cell_angle_beta                 70.549(4)
_cell_angle_gamma                88.791(4)
_cell_formula_units_Z            2
_cell_length_a                   10.5960(5)
_cell_length_b                   11.6796(5)
_cell_length_c                   12.6988(6)
_cell_measurement_reflns_used    8717
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      70.7680
_cell_measurement_theta_min      3.9570
_cell_volume                     1383.42(12)
_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      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.2312
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.986
_diffrn_measurement_details
;
  1 omega  -54.00    1.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000  -57.0000 -180.0000 55

  2 omega  -40.00    6.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000  -57.0000    0.0000 46

  3 omega  -86.00   -5.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      -33.5000  -77.0000  -60.0000 81

  4 omega  -48.00   34.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      -33.5000   37.0000  -30.0000 82

  5 omega   -4.00   72.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       36.4734  -99.0000  150.0000 76

  6 omega   -7.00   18.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       36.4734  105.0000   30.3643 25

  7 omega   24.00   72.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       36.4734  -99.0000   30.0000 48

  8 omega   34.00   76.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       36.4734 -113.0000  -72.0000 42

  9 omega   74.00  106.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       36.4734  178.0000   90.0000 32

 10 omega   11.00   44.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       36.4734  -99.0000 -120.0000 33

 11 omega   65.00  105.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       36.4734  178.0000 -180.0000 40

 12 omega    0.00   25.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       40.0000   98.0000  134.3213 25

 13 omega    7.00   32.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       44.0000   92.0000  -54.4753 25

 14 omega    8.00   33.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       44.0000   91.0000 -140.0348 25

 15 omega   15.00   40.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       48.0000   85.0000  124.6888 25

 16 omega   13.00   38.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       48.0000   88.0000  179.8351 25

 17 omega   21.00   46.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       52.0000   82.0000 -149.4447 25

 18 omega   20.00   45.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       52.0000   84.0000   10.6724 25

 19 omega   92.00  120.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       52.0000   78.0000  100.1606 28

 20 omega   20.00   45.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       52.0000   84.0000 -104.7758 25

 21 omega   23.00   49.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       52.0000   78.0000  100.1606 26

 22 omega   20.00   45.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       52.0000   83.0000  -65.4584 25

 23 omega   20.00   45.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       52.0000   84.0000  152.0584 25

 24 omega   28.00   54.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       56.0000   77.0000   54.1498 26

 25 omega   91.00  121.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       56.0000   77.0000   54.1498 30

 26 omega   29.00  124.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       56.0000   76.0000 -121.0811 95

 27 omega   33.00   72.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       60.0000   74.0000  -65.3547 39

 28 omega   40.00   78.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       60.0000   46.0000   97.6416 38

 29 omega   90.00  128.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       60.0000   74.0000  -65.3547 38

 30 omega   34.00   80.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       60.0000   72.0000  179.3593 46

 31 omega   34.00   60.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       60.0000   73.0000   -9.3855 26

 32 omega  107.00  133.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       64.0000   74.0000  116.0455 26

 33 omega   37.00   80.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       64.0000   74.0000  116.0455 43

 34 omega   46.00  127.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       68.0000   66.0000   18.4099 81

 35 omega   45.00  139.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       72.0000   74.0000  158.5692 94

 36 omega  111.00  140.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -       76.0000   52.0000  -21.4791 29

 37 omega   57.00   89.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -       76.0000   52.0000  -21.4791 32

 38 omega  110.00  176.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000 -180.0000 66

 39 omega   89.00  115.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   61.0000 -180.0000 26

 40 omega   79.00  104.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000 -180.0000 25

 41 omega   90.00  116.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   61.0000  -30.0000 26

 42 omega   90.00  167.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   61.0000  -90.0000 77

 43 omega   39.00   96.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -94.0000 -150.0000 57

 44 omega   43.00   93.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -94.0000   30.0000 50

 45 omega   80.00  177.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000  -60.0000 97

 46 omega  120.00  168.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000  150.0000 48

 47 omega   79.00  114.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000  150.0000 35

 48 omega   79.00  157.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000   90.0000 78

 49 omega   79.00  177.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000    0.0000 98

 50 omega  121.00  177.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000 -150.0000 56

 51 omega   79.00  105.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000 -150.0000 26

 52 omega   88.00  132.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   61.0000 -150.0000 44

 53 omega   55.00   97.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -94.0000  -90.0000 42

 54 omega   52.00  114.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000 -111.0000  120.0000 62

 55 omega  111.00  176.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000   60.0000 65

 56 omega   79.00  105.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000   60.0000 26

 57 omega   38.00  107.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -94.0000  -30.0000 69

 58 omega   79.00  104.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000  -90.0000 25

 59 omega   38.00   88.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -94.0000  150.0000 50

 60 omega   88.00  114.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   61.0000   60.0000 26

 61 omega   81.00  107.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000 -120.0000 26

 62 omega   89.00  114.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   61.0000   90.0000 25

 63 omega   79.00  167.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000  120.0000 88

 64 omega  130.00  175.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   61.0000 -120.0000 45

 65 omega   88.00  127.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   61.0000 -120.0000 39

 66 omega   79.00  156.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000  -30.0000 77

 67 omega  115.00  171.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000   30.0000 56

 68 omega   79.00  104.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000   30.0000 25
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.1172221000
_diffrn_orient_matrix_UB_12      0.0385618000
_diffrn_orient_matrix_UB_13      -0.1206260000
_diffrn_orient_matrix_UB_21      0.0970760000
_diffrn_orient_matrix_UB_22      0.0184155000
_diffrn_orient_matrix_UB_23      0.0614686000
_diffrn_orient_matrix_UB_31      0.0296420000
_diffrn_orient_matrix_UB_32      -0.1346712000
_diffrn_orient_matrix_UB_33      0.0255963000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0386
_diffrn_reflns_av_unetI/netI     0.0497
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.986
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            19847
_diffrn_reflns_point_group_measured_fraction_full 0.914
_diffrn_reflns_point_group_measured_fraction_max 0.893
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         70.931
_diffrn_reflns_theta_min         3.954
_diffrn_source                   'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.603
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.73294
_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            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.356
_exptl_crystal_description       prism
_exptl_crystal_F_000             588
_exptl_crystal_size_max          0.16
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.164
_refine_diff_density_min         -0.221
_refine_diff_density_rms         0.042
_refine_ls_abs_structure_details
;
 Flack x determined using 3308 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.004(10)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.051
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     743
_refine_ls_number_reflns         9547
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.051
_refine_ls_R_factor_all          0.0499
_refine_ls_R_factor_gt           0.0449
_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^)+(0.0588P)^2^+0.0252P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1108
_refine_ls_wR_factor_ref         0.1165
_reflns_Friedel_coverage         0.812
_reflns_Friedel_fraction_full    0.828
_reflns_Friedel_fraction_max     0.800
_reflns_number_gt                8701
_reflns_number_total             9547
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9qo00890j2.cif
_cod_data_source_block           201810421a
_cod_original_cell_volume        1383.43(12)
_cod_database_code               1555113
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C15H15O3N2Cl1
_shelx_estimated_absorpt_t_max   0.856
_shelx_estimated_absorpt_t_min   0.784
_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:
 C11(H11), C11'(H11'), C12(H12), C12'(H12')
2.b Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B), C9'(H9'A,H9'B), C16(H16A,H16B), C16'(H16C,H16D)
2.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C1'(H1'), C3(H3), C3'(H3'), C4(H4), C4'(H4'), C13(H13), C13'(H13'),
 C24(H24), C24'(H24'), C25(H25), C25'(H25'), C26(H26), C26'(H26'), C27(H27),
 C27'(H27'), C29(H29), C29'(H29'), C30(H30), C30'(H30'), C31(H31), C31'(H31'),
 C32(H32), C32'(H32'), C33(H33), C33'(H33')
2.d Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C), C10'(H10D,H10E,H10F), C17(H17A,H17B,H17C), C17'(H17D,
 H17E,H17F)
;
_olex2_submission_special_instructions 'No special instructions were received'