DABCO-Catalyzed Michael/Alkylation Cascade Reactions Involving α-Substituted Ammonium Ylides for the Construction of Spirocyclopropyl Oxindoles: Access to the Powerful Chemical Leads against HIV-1.
Chen, Lin; He, Jin; The Journal of organic chemistry  (2020) –; doi:10.1021/acs.joc.9b03164

data_4038186
_publ_section_title
;
 DABCO-Catalyzed Michael/Alkylation Cascade Reactions Involving
 \a-Substituted Ammonium Ylides for the Construction of Spirocyclopropyl
 Oxindoles: Access to the Powerful Chemical Leads against HIV-1.
;
_journal_name_full               'The Journal of organic chemistry'
_journal_paper_doi               10.1021/acs.joc.9b03164
_journal_year                    2020
_chemical_formula_moiety         'C13 H13 Br N2 O2'
_chemical_formula_sum            'C13 H13 Br N2 O2'
_chemical_formula_weight         309.16
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-12-18
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 99.809(16)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   8.0013(14)
_cell_length_b                   28.045(8)
_cell_length_c                   11.6926(19)
_cell_measurement_reflns_used    1398
_cell_measurement_temperature    292.65(10)
_cell_measurement_theta_max      69.9820
_cell_measurement_theta_min      3.1530
_cell_volume                     2585.4(10)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_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_environment      air
_diffrn_ambient_temperature      292.65(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2684
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.992
_diffrn_measured_fraction_theta_max 0.948
_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    -55.00  17.00   1.00    4.00    --  -40.92  38.00 -90.00   72
  2  \w     38.00  82.00   1.00    4.00    --   40.92-125.00 -30.00   44
  3  \w     66.00 133.00   1.00    5.00    --  106.95 -45.00 -30.00   67
  4  \w     64.00 106.00   1.00    5.00    --  106.95-111.00 120.00   42
  5  \w     80.00 177.00   1.00    5.00    --  106.95  30.00 150.00   97
  6  \w    117.00 143.00   1.00    5.00    --  106.95 111.00 -60.00   26
  7  \w    148.00 174.00   1.00    5.00    --  106.95 111.00-180.00   26
  8  \w     84.00 125.00   1.00    5.00    --  106.95 178.00-120.00   41
  9  \w     80.00 151.00   1.00    5.00    --  106.95 178.00 120.00   71
 10  \w     35.00 111.00   1.00    5.00    --  106.95-111.00-150.00   76
 11  \w   -111.00 -27.00   1.00    4.00    --  -40.92 -19.00 -90.00   84
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0963663000
_diffrn_orient_matrix_UB_12      -0.0076998000
_diffrn_orient_matrix_UB_13      0.1244338000
_diffrn_orient_matrix_UB_21      0.0322131000
_diffrn_orient_matrix_UB_22      0.0540699000
_diffrn_orient_matrix_UB_23      0.0127997000
_diffrn_orient_matrix_UB_31      -0.1671537000
_diffrn_orient_matrix_UB_32      0.0059855000
_diffrn_orient_matrix_UB_33      0.0469908000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0608
_diffrn_reflns_av_unetI/netI     0.3062
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.948
_diffrn_reflns_limit_h_max       5
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       33
_diffrn_reflns_limit_k_min       -34
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            9200
_diffrn_reflns_point_group_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.948
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.203
_diffrn_reflns_theta_min         3.152
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.311
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.64905
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43f (Rigaku Oxford Diffraction, 2015)
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    1.589
_exptl_crystal_description       block
_exptl_crystal_F_000             1248
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.272
_refine_diff_density_min         -1.006
_refine_diff_density_rms         0.416
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.031
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     329
_refine_ls_number_reflns         4975
_refine_ls_number_restraints     216
_refine_ls_restrained_S_all      1.798
_refine_ls_R_factor_all          0.0870
_refine_ls_R_factor_gt           0.0664
_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^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1698
_refine_ls_wR_factor_ref         0.1998
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2750
_reflns_number_total             4975
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo9b03164_si_001.cif
_cod_data_source_block           h1813
_cod_database_code               4038186
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.672
_shelx_estimated_absorpt_t_min   0.604
_reflns_odcompleteness_completeness 99.09
_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 N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(C1) \\sim Ueq, Uanis(C2) \\sim Ueq, Uanis(C3) \\sim Ueq, Uanis(C4) \\sim
Ueq, Uanis(C5) \\sim Ueq, Uanis(C6) \\sim Ueq, Uanis(C7) \\sim Ueq, Uanis(C8)
\\sim Ueq, Uanis(C9) \\sim Ueq: with sigma of 0.002 and sigma for terminal
atoms of 0.004
Uanis(C10) \\sim Ueq, Uanis(C11) \\sim Ueq, Uanis(C12) \\sim Ueq, Uanis(C13)
\\sim Ueq, Uanis(N1) \\sim Ueq, Uanis(N2) \\sim Ueq, Uanis(O1) \\sim Ueq,
Uanis(O2) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
Uanis(C1) \\sim Ueq, Uanis(Br1) \\sim Ueq: with sigma of 0.0005 and sigma for
terminal atoms of 0.001
Uanis(C1B) \\sim Ueq, Uanis(C2B) \\sim Ueq, Uanis(C3B) \\sim Ueq, Uanis(C4B)
\\sim Ueq, Uanis(C5B) \\sim Ueq, Uanis(C6B) \\sim Ueq, Uanis(C7B) \\sim Ueq,
Uanis(C8B) \\sim Ueq, Uanis(C9B) \\sim Ueq, Uanis(C10B) \\sim Ueq, Uanis(C11B)
\\sim Ueq, Uanis(C12B) \\sim Ueq, Uanis(C13B) \\sim Ueq: with sigma of 0.002
and sigma for terminal atoms of 0.004
Uanis(N1B) \\sim Ueq, Uanis(N2B) \\sim Ueq, Uanis(O1B) \\sim Ueq, Uanis(O2B)
\\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
Uanis(Br1B) \\sim Ueq: with sigma of 0.0002 and sigma for terminal atoms of
0.0004
Uanis(Br1) \\sim Ueq: with sigma of 0.0001 and sigma for terminal atoms of
0.0002
3.a Ternary CH refined with riding coordinates:
 C9(H9), C10(H10), C9B(H9B), C10B(H10B)
3.b Aromatic/amide H refined with riding coordinates:
 N2B(H2B), N1(H1), N1B(H1B), C2(H2), N2(H2A), C3(H3), C6B(H6B), C3B(H3B),
 C2B(H2BA), C6(H6)
3.c Idealised Me refined as rotating group:
 C13(H13D,H13E,H13F), C12(H12A,H12B,H12C), C13B(H13A,H13B,H13C), C11B(H11A,
 H11B,H11C)
;
_olex2_date_sample_data_collection 2018-12-18
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Frame scaling
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 2.522
_oxdiff_exptl_absorpt_empirical_full_min 0.501