Enantioselective synthesis of spirooxindole-pyran derivatives <i>via</i> a remote inverse-electron-demand Diels-Alder reaction of β,γ-unsaturated amides.
Chen, Yuzhen; Chen, Jiajia; Zhong, Lin; Zhang, Yili; Zhan, Ruoting; Huang, Huicai; Xue, Yongbo; Organic & biomolecular chemistry 22 (2024) 3198–3203; doi:10.1039/d4ob00303a

data_7159858
_publ_section_title
;
 Enantioselective synthesis of spirooxindole-pyran derivatives <i>via</i>
 a remote inverse-electron-demand Diels-Alder reaction of
 &#x3b2;,&#x3b3;-unsaturated amides.
;
_journal_issue                   16
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              3198
_journal_page_last               3203
_journal_paper_doi               10.1039/d4ob00303a
_journal_volume                  22
_journal_year                    2024
_chemical_formula_moiety         'C55 H39 Br N4 O3, C3 H7'
_chemical_formula_sum            'C58 H46 Br N4 O3'
_chemical_formula_weight         926.90
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2021-01-11
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2021-04-01 deposited with the CCDC.	2024-03-19 downloaded from the CCDC.
;
_cell_angle_alpha                103.7952(18)
_cell_angle_beta                 102.2696(18)
_cell_angle_gamma                93.4841(16)
_cell_formula_units_Z            2
_cell_length_a                   11.2020(2)
_cell_length_b                   11.3554(2)
_cell_length_c                   18.8713(4)
_cell_measurement_reflns_used    16860
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      75.9800
_cell_measurement_theta_min      4.0630
_cell_volume                     2262.23(8)
_computing_cell_refinement       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.959
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w    -64.00  22.00   0.50    0.15    --  -46.00  82.00 131.00  172
  2  \w    -25.00  27.00   0.50    0.15    --  -46.00  19.00  30.00  104
  3  \w    -40.00  26.00   0.50    0.15    --  -46.00  37.00  60.00  132
  4  \w    -56.00 -30.00   0.50    0.61    -- -102.00  82.00 131.00   52
  5  \w    -67.00 -29.00   0.50    0.61    -- -102.00  77.00  60.00   76
  6  \w    -97.00 -72.00   0.50    0.61    -- -102.00  77.00  60.00   50
  7  \w   -108.00 -58.00   0.50    0.61    -- -102.00 109.00  77.81  100
  8  \w   -108.00 -43.00   0.50    0.61    -- -102.00 110.00 -92.50  130
  9  \w    -76.00 -45.00   0.50    0.61    -- -102.00 125.00-120.00   62
 10  \w    -65.00 -33.00   0.50    0.61    -- -102.00  61.00-150.00   64
 11  \w   -108.00 -80.00   0.50    0.61    -- -102.00 125.00-120.00   56
 12  \w   -174.00-138.00   0.50    0.61    -- -102.00 -15.00-150.00   72
 13  \w   -134.00-105.00   0.50    0.61    -- -102.00 -15.00-150.00   58
 14  \w   -123.00 -87.00   0.50    0.61    -- -102.00 -61.00 -30.00   72
 15  \w   -155.00 -81.00   0.50    0.61    -- -102.00 -82.00  10.00  148
 16  \w   -118.00 -81.00   0.50    0.15    --  -46.00-125.00 120.00   74
 17  \w   -106.00 -74.00   0.50    0.15    --  -46.00-125.00 150.00   64
 18  \w   -136.00 -91.00   0.50    0.61    -- -102.00 -94.00 120.00   90
 19  \w   -173.00-146.00   0.50    0.61    -- -102.00 -94.00 120.00   54
 20  \w   -158.00-133.00   0.50    0.61    -- -102.00 -61.00 -30.00   50
 21  \w   -113.00 -87.00   0.50    0.15    --  -46.00-125.00-150.00   52
 22  \w     -1.00  70.00   0.50    0.15    --   46.00 -82.00  10.00  142
 23  \w     70.00  96.00   0.50    0.61    --  106.06 -82.00  10.00   52
 24  \w     82.00 108.00   0.50    0.61    --  106.06-125.00  60.00   52
 25  \w     59.00  96.00   0.50    0.61    --  106.06-125.00 120.00   74
 26  \w     34.00 112.00   0.50    0.61    --  106.06-125.00  90.00  156
 27  \w     33.00  68.00   0.50    0.61    --  106.06-125.00  60.00   70
 28  \w     37.00 112.00   0.50    0.61    --  106.06-125.00   0.00  150
 29  \w     85.00 112.00   0.50    0.61    --  106.06-125.00 -90.00   54
 30  \w     74.00 103.00   0.50    0.61    --  106.06 -94.00-180.00   58
 31  \w     40.00 116.00   0.50    0.61    --  106.06-134.00-144.23  152
 32  \w     38.00  71.00   0.50    0.61    --  106.06-125.00 -90.00   66
 33  \w     35.00  72.00   0.50    0.61    --  106.06 -61.00-150.00   74
 34  \w    105.00 176.00   0.50    0.61    --  106.06  30.00 -90.00  142
 35  \w    132.00 158.00   0.50    0.61    --  106.06 125.00 -30.00   52
 36  \w     92.00 178.00   0.50    0.61    --  106.06  45.00  90.00  172
 37  \w    149.00 175.00   0.50    0.61    --  106.06  82.00 131.00   52
 38  \w     84.00 145.00   0.50    0.61    --  106.06  82.00 131.00  122
 39  \w     84.00 121.00   0.50    0.61    --  106.06 125.00 -30.00   74
 40  \w     93.00 176.00   0.50    0.61    --  106.06  45.00-150.00  166
 41  \w     33.00  72.00   0.50    0.61    --  106.06 -94.00 150.00   78
 42  \w     38.00 112.00   0.50    0.61    --  106.06-125.00 150.00  148
 43  \w     -8.00  17.00   0.50    0.15    --   46.00 -19.00  90.00   50
 44  \w    -25.00  29.00   0.50    0.15    --   46.00 -19.00-150.00  108
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1087797000
_diffrn_orient_matrix_UB_12      -0.1019649000
_diffrn_orient_matrix_UB_13      -0.0243786000
_diffrn_orient_matrix_UB_21      0.0441536000
_diffrn_orient_matrix_UB_22      -0.0560925000
_diffrn_orient_matrix_UB_23      -0.0713028000
_diffrn_orient_matrix_UB_31      0.0793878000
_diffrn_orient_matrix_UB_32      -0.0790266000
_diffrn_orient_matrix_UB_33      0.0423992000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0476
_diffrn_reflns_av_unetI/netI     0.0468
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.959
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            30212
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.959
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.073
_diffrn_reflns_theta_min         2.480
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.649
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.81403
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.84a (Rigaku Oxford Diffraction, 2020)
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    1.361
_exptl_crystal_description       block
_exptl_crystal_F_000             962
_exptl_crystal_size_max          0.05
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.03
_refine_diff_density_max         1.963
_refine_diff_density_min         -0.847
_refine_diff_density_rms         0.114
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.065
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     596
_refine_ls_number_reflns         9179
_refine_ls_number_restraints     18
_refine_ls_restrained_S_all      1.079
_refine_ls_R_factor_all          0.0798
_refine_ls_R_factor_gt           0.0733
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1291P)^2^+3.9844P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2054
_refine_ls_wR_factor_ref         0.2130
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8080
_reflns_number_total             9179
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4ob00303a2.cif
_cod_data_source_block           yz0644-1
_cod_depositor_comments          'Adding full bibliography for 7159858.cif.'
_cod_original_cell_volume        2262.21(8)
_cod_database_code               7159858
_shelx_shelxl_version_number     2018/1
_chemical_oxdiff_formula         'C N O Br'
_shelx_estimated_absorpt_t_max   0.952
_shelx_estimated_absorpt_t_min   0.922
_diffrn_oxdiff_digest_frames
;
01fce61d438b5a26161774741f64d7c55603996c70c
;
_diffrn_oxdiff_digest_hkl
;
015908d84f5a015dba7fb6d45251841b7dce4a
;
_reflns_odcompleteness_completeness 99.96
_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. Uiso/Uaniso restraints and constraints
Uanis(C21) \\sim Ueq, Uanis(C19) \\sim Ueq, Uanis(C58) \\sim Ueq, Uanis(C58)
\\sim Ueq: with sigma of 0.004 and sigma for terminal atoms of 0.008
3.a Ternary CH refined with riding coordinates:
 C23(H23), C22(H22), C9(H9)
3.b Secondary CH2 refined with riding coordinates:
 C38(H38A,H38B), C56(H56A,H56B), C57(H57A,H57B)
3.c Aromatic/amide H refined with riding coordinates:
 C55(H55), C27(H27), C28(H28), C48(H48), C37(H37), C33(H33), C54(H54),
 C42(H42), C52(H52), C51(H51), C15(H15), C53(H53), C30(H30), C5(H5), C14(H14),
 C45(H45), C43(H43), C46(H46), C36(H36), C34(H34), C44(H44), C31(H31), C11(H11),
  C35(H35), C13(H13), C4(H4), C12(H12), C2(H2), C3(H3), C21(H21), C17(H17),
 C20(H20), C18(H18), C19(H19)
3.d Idealised Me refined as rotating group:
 C58(H58A,H58B,H58C)
;
_shelx_res_checksum              41002
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.641
_oxdiff_exptl_absorpt_empirical_full_min 0.642