Asymmetric Synthesis of Spirocyclic Oxindole δ-Lactams via NHC-Catalyzed Formal [2+4] Annulation of Aliphatic Aldehydes with Oxindole-Derived α,β-Unsaturated Ketimines.
He, Chonglong; Li, Zhanhuan; Xu, Jianfeng; Ren, Hongjun; The Journal of organic chemistry 84 (2019) 12177–12186; doi:10.1021/acs.joc.9b01760

data_4034492
_publ_section_title
;
 Asymmetric Synthesis of Spirocyclic Oxindole \d-Lactams via NHC-Catalyzed
 Formal [2+4] Annulation of Aliphatic Aldehydes with Oxindole-Derived
 \a,\b-Unsaturated Ketimines.
;
_journal_issue                   18
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              12177
_journal_page_last               12186
_journal_paper_doi               10.1021/acs.joc.9b01760
_journal_volume                  84
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C34 H30 N2 O5 S'
_chemical_formula_sum            'C34 H30 N2 O5 S'
_chemical_formula_weight         578.66
_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             2018-12-21
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.19250(10)
_cell_length_b                   19.2110(5)
_cell_length_c                   20.7806(5)
_cell_measurement_reflns_used    9810
_cell_measurement_temperature    170(2)
_cell_measurement_theta_max      31.95
_cell_measurement_theta_min      2.23
_cell_volume                     2871.36(11)
_computing_cell_refinement       'SAINT V8.38A (?, 2016)'
_computing_data_reduction        'SAINT V8.38A (?, 2016)'
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      170.0
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0375
_diffrn_reflns_av_unetI/netI     0.0348
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            41901
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         32.045
_diffrn_reflns_theta_min         2.336
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.159
_exptl_absorpt_correction_T_max  0.7463
_exptl_absorpt_correction_T_min  0.6521
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0725 before and 0.0610 after correction.
The Ratio of minimum to maximum transmission is 0.8738.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.339
_exptl_crystal_description       block
_exptl_crystal_F_000             1216
_exptl_crystal_size_max          0.476
_exptl_crystal_size_mid          0.33
_exptl_crystal_size_min          0.319
_refine_diff_density_max         0.236
_refine_diff_density_min         -0.382
_refine_diff_density_rms         0.047
_refine_ls_abs_structure_details
;
 Flack x determined using 3458 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.01(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.039
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     382
_refine_ls_number_reflns         10009
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.039
_refine_ls_R_factor_all          0.0476
_refine_ls_R_factor_gt           0.0390
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0445P)^2^+0.5190P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0910
_refine_ls_wR_factor_ref         0.0979
_reflns_Friedel_coverage         0.792
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.999
_reflns_number_gt                8871
_reflns_number_total             10009
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo9b01760_si_002.cif
_cod_data_source_block           181220_hcl_2_4_0m
_cod_database_code               4034492
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.951
_shelx_estimated_absorpt_t_min   0.928
_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:
 C12(H12)
2.b Secondary CH2 refined with riding coordinates:
 C28(H28A,H28B)
2.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C3(H3), C4(H4), C9(H9), C16(H16), C17(H17), C18(H18), C19(H19),
 C20(H20), C22(H22), C23(H23), C25(H25), C26(H26), C30(H30), C31(H31), C32(H32),
  C33(H33), C34(H34)
2.d Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C27(H27A,H27B,H27C)
;
_shelx_res_checksum              89221
_shelx_hkl_checksum              70285
_olex2_submission_special_instructions 'No special instructions were received'