A quinine-squaramide catalyzed enantioselective vinylogous Mannich reaction between benzothiazolimines and γ-butenolides for efficient preparation of chiral N-benzothiazole butyrolactones
Yu, Jing-Liang; Zhang, Qian-Mao; Cheng, Guo; Tang, Chun-Chun; Yang, Zhen-Yu; Li, Wen-Sheng; Wang, Li-Xin; Organic & Biomolecular Chemistry 22 (2024) 7612–7617; doi:10.1039/D4OB01175A

data_7160105
_publ_section_title
;
 A quinine-squaramide catalyzed enantioselective vinylogous Mannich
 reaction between benzothiazolimines and \g-butenolides for efficient
 preparation of chiral N-benzothiazole butyrolactones
;
_journal_issue                   37
_journal_name_full               'Organic &amp; Biomolecular Chemistry'
_journal_page_first              7612
_journal_page_last               7617
_journal_paper_doi               10.1039/D4OB01175A
_journal_volume                  22
_journal_year                    2024
_chemical_absolute_configuration ad
_chemical_formula_moiety         '2(C25 H19 Cl N2 O2 S), C H2 Cl2'
_chemical_formula_sum            'C51 H40 Cl4 N4 O4 S2'
_chemical_formula_weight         978.79
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2024-03-11
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2024-03-13 deposited with the CCDC.	2024-08-21 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 109.741(4)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   15.8968(6)
_cell_length_b                   11.2913(4)
_cell_length_c                   16.5092(6)
_cell_measurement_reflns_used    6098
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      66.0100
_cell_measurement_theta_min      3.9110
_cell_volume                     2789.17(19)
_computing_cell_refinement       'CrysAlisPro 1.171.42.81a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.81a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.81a (Rigaku OD, 2023)'
_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 0.998
_diffrn_measured_fraction_theta_max 0.985
_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    -93.00 -35.00   1.00    2.00    --  -33.50 178.00-180.00   58
  2  \w   -107.00 -38.00   1.00    2.00    --  -33.50 178.00  60.00   69
  3  \w    -89.00 -62.00   1.00    2.00    --  -33.50 -48.00  14.10   27
  4  \w   -100.00 -22.00   1.00    2.00    --  -33.50 -62.00  85.55   78
  5  \w    -53.00 -26.00   1.00    2.00    --  -33.50 -61.00 -54.67   27
  6  \w    -93.00 -60.00   1.00    2.00    --  -33.50 -61.00 -54.67   33
  7  \w    -53.00 -26.00   1.00    2.00    --  -33.50 -72.00 154.23   27
  8  \w    -55.00 -11.00   1.00    2.00    --  -33.50 -37.00 -90.00   44
  9  \w    -27.00  28.00   1.00    2.00    --  -33.50  37.00-120.00   55
 10  \w    -45.00 -15.00   1.00    2.00    --  -33.50 -48.00  14.10   30
 11  \w    -57.00 -12.00   1.00    2.00    --  -33.50 -37.00 120.00   45
 12  \w   -102.00 -61.00   1.00    2.00    --  -33.50 -37.00 120.00   41
 13  \w    -50.00 -15.00   1.00    2.00    --  -33.50 -57.00-180.00   35
 14  \w     -1.00  24.00   1.00    2.00    --   36.47  93.00  83.45   25
 15  \w      0.00  27.00   1.00    2.00    --   36.47  93.00 116.53   27
 16  \w     23.00  50.00   1.00    2.00    --   36.47 -99.00 150.00   27
 17  \w     -2.00  23.00   1.00    2.00    --   36.47  95.00 152.74   25
 18  \w     36.00  89.00   1.00    2.00    --   36.47-142.00 147.00   53
 19  \w     89.00 114.00   1.00   12.00    --  108.00  45.00   0.00   25
 20  \w    140.00 166.00   1.00   12.00    --  108.00  61.00 120.00   26
 21  \w    130.00 175.00   1.00   12.00    --  108.00  61.00  90.00   45
 22  \w     88.00 115.00   1.00   12.00    --  108.00  61.00  90.00   27
 23  \w     88.00 115.00   1.00   12.00    --  108.00  61.00  60.00   27
 24  \w     64.00  91.00   1.00   12.00    --  108.00  15.00  30.00   27
 25  \w    130.00 174.00   1.00   12.00    --  108.00  61.00  60.00   44
 26  \w     88.00 115.00   1.00   12.00    --  108.00  61.00 120.00   27
 27  \w     88.00 114.00   1.00   12.00    --  108.00  45.00  60.00   26
 28  \w     82.00 110.00   1.00   12.00    --  108.00  30.00 120.00   28
 29  \w     66.00 105.00   1.00   12.00    --  108.00 -94.00   0.00   39
 30  \w     65.00  92.00   1.00   12.00    --  108.00-111.00 120.00   27
 31  \w     82.00 108.00   1.00   12.00    --  108.00  30.00  90.00   26
 32  \w     38.00 106.00   1.00   12.00    --  108.00 -94.00-120.00   68
 33  \w    141.00 167.00   1.00   12.00    --  108.00  61.00   0.00   26
 34  \w     89.00 114.00   1.00   12.00    --  108.00  45.00 120.00   25
 35  \w     88.00 114.00   1.00   12.00    --  108.00  45.00  90.00   26
 36  \w     88.00 129.00   1.00   12.00    --  108.00  61.00   0.00   41
 37  \w    101.00 134.00   1.00   12.00    --  108.00 178.00 -60.00   33
 38  \w     86.00 115.00   1.00   12.00    --  108.00  30.00   0.00   29
 39  \w     88.00 115.00   1.00   12.00    --  108.00  45.00 150.00   27
 40  \w     89.00 175.00   1.00   12.00    --  108.00  61.00 150.00   86
 41  \w     88.00 156.00   1.00   12.00    --  108.00  45.00  30.00   68
 42  \w     82.00 109.00   1.00   12.00    --  108.00  30.00  60.00   27
 43  \w     83.00 115.00   1.00   12.00    --  108.00  30.00  30.00   32
 44  \w     82.00 109.00   1.00   12.00    --  108.00  30.00-180.00   27
 45  \w     82.00 113.00   1.00   12.00    --  108.00  30.00 150.00   31
 46  \w     62.00  97.00   1.00   12.00    --  108.00 178.00 -60.00   35
 47  \w     40.00 128.00   1.00   12.00    --  108.00 -61.00-120.00   88
 48  \w     66.00  93.00   1.00   12.00    --  108.00  15.00  60.00   27
 49  \w     65.00  95.00   1.00   12.00    --  108.00  15.00  90.00   30
 50  \w     88.00 172.00   1.00   12.00    --  108.00  61.00  30.00   84
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0275301000
_diffrn_orient_matrix_UB_12      -0.0078774000
_diffrn_orient_matrix_UB_13      0.0986833000
_diffrn_orient_matrix_UB_21      -0.0981192000
_diffrn_orient_matrix_UB_22      -0.0225102000
_diffrn_orient_matrix_UB_23      -0.0081524000
_diffrn_orient_matrix_UB_31      0.0147902000
_diffrn_orient_matrix_UB_32      -0.1343692000
_diffrn_orient_matrix_UB_33      -0.0044307000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0461
_diffrn_reflns_av_unetI/netI     0.0588
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            24007
_diffrn_reflns_point_group_measured_fraction_full 0.889
_diffrn_reflns_point_group_measured_fraction_max 0.871
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         70.419
_diffrn_reflns_theta_min         4.745
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.970
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.39973
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.81a (Rigaku Oxford Diffraction, 2023)
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    1.165
_exptl_crystal_description       plate
_exptl_crystal_F_000             1012
_exptl_crystal_size_max          0.17
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.605
_refine_diff_density_min         -0.273
_refine_diff_density_rms         0.087
_refine_ls_abs_structure_details
;
 Flack x determined using 1892 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   1.027
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     556
_refine_ls_number_reflns         9306
_refine_ls_number_restraints     67
_refine_ls_restrained_S_all      1.030
_refine_ls_R_factor_all          0.1093
_refine_ls_R_factor_gt           0.0890
_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^)+(0.1651P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2295
_refine_ls_wR_factor_ref         0.2561
_reflns_Friedel_coverage         0.677
_reflns_Friedel_fraction_full    0.767
_reflns_Friedel_fraction_max     0.744
_reflns_number_gt                6656
_reflns_number_total             9306
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4ob01175a2.cif
_cod_data_source_block           20240373
_cod_depositor_comments          'Adding full bibliography for 7160105.cif.'
_cod_database_code               7160105
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C20H20N4S1Cl1
_shelx_estimated_absorpt_t_max   0.797
_shelx_estimated_absorpt_t_min   0.632
_reflns_odcompleteness_completeness 99.90
_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. Restrained distances
 C26A-Cl2A
 1.75 with sigma of 0.02
 C26A-Cl3A
 1.75 with sigma of 0.02
 Cl3A-Cl2A
 2.8 with sigma of 0.02
 C4'-C5'A
 1.54 with sigma of 0.02
 C3-C2
 1.4 with sigma of 0.02
 C3'-C2'
 1.4 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C7') \\sim Ueq, Uanis(C6') \\sim Ueq, Uanis(C5') \\sim Ueq, Uanis(C10')
\\sim Ueq, Uanis(C9') \\sim Ueq, Uanis(C8') \\sim Ueq, Uanis(Cl1') \\sim Ueq:
with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(Cl2) \\sim Ueq, Uanis(C26) \\sim Ueq, Uanis(Cl3) \\sim Ueq: with sigma of
0.1 and sigma for terminal atoms of 0.2
Uanis(C5') = Uanis(C5'A)
Uanis(C10') = Uanis(C1A)
Uanis(C9') = Uanis(C9'A)
Uanis(C8') = Uanis(C8'A)
Uanis(C7') = Uanis(C7'A)
Uanis(C6') = Uanis(C6'A)
Uanis(Cl1') = Uanis(Cl1B)
Uanis(C26) = Uanis(C26A)
Uanis(Cl2) = Uanis(Cl2A)
Uanis(Cl3) = Uanis(Cl3A)
4. Others
 Sof(Cl1B)=Sof(C6'A)=Sof(H6'A)=Sof(C7'A)=Sof(H7'A)=Sof(C8'A)=Sof(C9'A)=
 Sof(H9'A)=Sof(C1A)=Sof(H1A)=Sof(C5'A)=1-FVAR(1)
 Sof(Cl1')=Sof(C5')=Sof(C6')=Sof(H6')=Sof(C7')=Sof(H7')=Sof(C8')=Sof(C9')=
 Sof(H9')=Sof(C10')=Sof(H10')=FVAR(1)
 Sof(Cl2A)=Sof(Cl3A)=Sof(C26A)=Sof(H26C)=Sof(H26D)=1-FVAR(2)
 Sof(Cl2)=Sof(Cl3)=Sof(C26)=Sof(H26A)=Sof(H26B)=FVAR(2)
5.a Ternary CH refined with riding coordinates:
 C11'(H11'), C11(H11)
5.b Secondary CH2 refined with riding coordinates:
 C26(H26A,H26B), C26A(H26C,H26D)
5.c Aromatic/amide H refined with riding coordinates:
 C3'(H3'), C6'(H6'), C7'(H7'), C9'(H9'), C10'(H10'), C6'A(H6'A), C7'A(H7'A),
 C9'A(H9'A), C1A(H1A), C13'(H13'), C14'(H14'), C15'(H15'), C16'(H16'),
 C17'(H17'), C22'(H22'), C23'(H23'), C24'(H24'), C25'(H25'), C3(H3), C10(H10),
 C9(H9), C7(H7), C6(H6), C13(H13), C14(H14), C15(H15), C16(H16), C17(H17),
 C22(H22), C23(H23), C24(H24), C25(H25)
5.d Fitted hexagon refined as free rotating group:
 C5'(C6',C7',C8',C9',C10'), C6'A(C7'A,C8'A,C9'A,C1A,C5'A), C12'(C13',C14',C15',
 C16',C17'), C20'(C21',C22',C23',C24',C25'), C10(C9,C8,C7,C6,C5), C20(C21,C22,
 C23,C24,C25)
5.e Idealised Me refined as rotating group:
 C18'(H18A,H18B,H18C), C18(H18D,H18E,H18F)
;
_shelx_res_checksum              85132
_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 3.853
_oxdiff_exptl_absorpt_empirical_full_min 0.548