Asymmetric synthesis of isoxazole and trifluoromethyl-containing 3,2'-pyrrolidinyl dispirooxindoles <i>via</i> squaramide-catalysed [3 + 2] cycloaddition reactions.
Li, Tong-Hao; Du, Da-Ming; Organic & biomolecular chemistry 20 (2022) 817–823; doi:10.1039/d1ob02350k

data_7158458
_publ_section_title
;
 Asymmetric synthesis of isoxazole and trifluoromethyl-containing
 3,2'-pyrrolidinyl dispirooxindoles <i>via</i> squaramide-catalysed [3 +
 2] cycloaddition reactions.
;
_journal_issue                   4
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              817
_journal_page_last               823
_journal_paper_doi               10.1039/d1ob02350k
_journal_volume                  20
_journal_year                    2022
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C37 H27 Br F3 N5 O5'
_chemical_formula_sum            'C37 H27 Br F3 N5 O5'
_chemical_formula_weight         758.54
_chemical_melting_point          474.0(10)
_chemical_name_systematic
(3R,3'R,4'S,5'S)-1,1''-Dibenzyl-7-bromo-4'-(3-methyl-4-nitroisoxazol-5-yl)-5'-(trifluoromethyl)dispiro[indoline-3,2'-pyrrolidine-3',3''-indoline]-2,2''-dione
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-11-30
_audit_creation_method
;
Olex2 1.5
(compiled 2021.07.19 svn.r715e62df for OlexSys, GUI svn.r6383)
;
_audit_update_record
;
2021-12-01 deposited with the CCDC.	2021-12-22 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.7153(9)
_cell_length_b                   14.2963(12)
_cell_length_c                   24.322(2)
_cell_measurement_reflns_used    9419
_cell_measurement_temperature    298.00
_cell_measurement_theta_max      53.63
_cell_measurement_theta_min      3.12
_cell_volume                     3378.2(5)
_computing_cell_refinement       'SAINT V8.38A (Bruker, 2018)'
_computing_data_reduction        'SAINT V8.38A (Bruker, 2018)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      298.00
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           GaK\a
_diffrn_radiation_wavelength     1.34139
_diffrn_reflns_av_R_equivalents  0.0631
_diffrn_reflns_av_unetI/netI     0.0181
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            181597
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        53.594
_diffrn_reflns_theta_max         57.107
_diffrn_reflns_theta_min         3.119
_diffrn_source_current           2.23
_diffrn_source_power             0.1557878
_diffrn_source_voltage           69.86
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.473
_exptl_absorpt_correction_T_max  0.7512
_exptl_absorpt_correction_T_min  0.5683
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1568 before and 0.0663 after correction.
The Ratio of minimum to maximum transmission is 0.7565.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.491
_exptl_crystal_description       block
_exptl_crystal_F_000             1544
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: toluene'
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.16
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.352
_refine_diff_density_min         -0.984
_refine_diff_density_rms         0.062
_refine_ls_abs_structure_details
;
 Flack x determined using 2458 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.008(4)
_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     461
_refine_ls_number_reflns         6915
_refine_ls_number_restraints     792
_refine_ls_restrained_S_all      1.059
_refine_ls_R_factor_all          0.0490
_refine_ls_R_factor_gt           0.0417
_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^)+(0.0562P)^2^+1.6230P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1028
_refine_ls_wR_factor_ref         0.1078
_reflns_Friedel_coverage         0.779
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.996
_reflns_number_gt                6132
_reflns_number_total             6915
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1ob02350k2.cif
_cod_data_source_block           1_a
_cod_depositor_comments
;
The following automatic conversions were performed:

data item '_chemical_melting_point' value '473-475' was changed to
'474.0(10)' -- the average value was taken and precision was
estimated.

Automatic conversion script
Id: cif_fix_values 7556 2019-12-06 15:28:31Z antanas 

 Adding full bibliography for 7158458.cif.
;
_cod_database_code               7158458
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
F1 \\sim F2 \\sim F3 \\sim O1 \\sim O2 \\sim O5 \\sim O4 \\sim N1 \\sim N2
\\sim N3 \\sim N4 \\sim N5 \\sim C1 \\sim Br1 \\sim O3 \\sim C4 \\sim C5 \\sim
C6 \\sim C7 \\sim C8 \\sim C9 \\sim C10 \\sim C11 \\sim C12 \\sim C13 \\sim C14
\\sim C15 \\sim C16 \\sim C17 \\sim C18 \\sim C19 \\sim C1A \\sim C20 \\sim C21
\\sim C22 \\sim C23 \\sim C24 \\sim C25 \\sim C26 \\sim C27 \\sim C28 \\sim C29
\\sim C30 \\sim C31 \\sim C32 \\sim C33 \\sim C34 \\sim C35 \\sim C36 \\sim C37
\\sim C38: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
within 2A
3. Rigid body (RIGU) restrains
 F1, F2, F3, O1, O2, O5, O4, N1, N2, N3, N4, N5, C1, Br1, O3, C4, C5, C6, C7,
 C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, C1A, C20, C21, C22,
 C23, C24, C25, C26, C27, C28, C29, C30, C31, C32, C33, C34, C35, C36, C37, C38
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
4.a Ternary CH refined with riding coordinates:
 C12(H12), C16(H16)
4.b Secondary CH2 refined with riding coordinates:
 C17(H17A,H17B), C1A(H1AA,H1AB)
4.c Aromatic/amide H refined with riding coordinates:
 N4(H4), C8(H8), C15(H15), C18(H18), C20(H20), C22(H22), C24(H24), C25(H25),
 C26(H26), C29(H29), C30(H30), C31(H31), C32(H32), C33(H33), C34(H34), C36(H36),
  C37(H37), C38(H38)
4.d Idealised Me refined as rotating group:
 C35(H35A,H35B,H35C)
;
_olex2_submission_special_instructions 'No special instructions were received'