Magnesium catalyzed [3 + 3] heteroannulation of α-enolic dithioesters with MBH acetate: access to functionalized 3,4-dihydro-2H-thiopyrans
Soni, Sonam; Shukla, Gaurav; Singh, Maya Shankar; Organic & Biomolecular Chemistry  (2022) –; doi:10.1039/D2OB01258H

data_7158823
_publ_section_title
;
 Magnesium catalyzed [3 + 3] heteroannulation of \a-enolic dithioesters
 with MBH acetate: access to functionalized 3,4-dihydro-2H-thiopyrans
;
_journal_name_full               'Organic &amp; Biomolecular Chemistry'
_journal_paper_doi               10.1039/D2OB01258H
_journal_year                    2022
_chemical_absolute_configuration unk
_chemical_formula_moiety         'C21 H16 F3 N O S2'
_chemical_formula_sum            'C21 H16 F3 N O S2'
_chemical_formula_weight         419.495
_space_group_crystal_system      trigonal
_space_group_IT_number           146
_space_group_name_Hall           'R 3'
_space_group_name_H-M_alt        'R 3 :H'
_symmetry_Int_Tables_number      146
_atom_sites_solution_primary     iterative
_audit_creation_date             2021-07-11
_audit_creation_method
;
Olex2 1.3-beta
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_audit_update_record
;
2021-07-15 deposited with the CCDC.	2022-08-03 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            9
_cell_length_a                   29.2329(6)
_cell_length_b                   29.2329(6)
_cell_length_c                   6.01889(12)
_cell_measurement_reflns_used    3765
_cell_measurement_temperature    298(2)
_cell_measurement_theta_max      68.0950
_cell_measurement_theta_min      3.0190
_cell_volume                     4454.42(16)
_computing_cell_refinement       'CrysAlisPro 1.171.41.96a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.96a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.96a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.3-beta (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-beta (Dolomanov et al., 2009)'
_computing_structure_refinement  'olex2.refine 1.3-beta (Bourhis et al., 2015)'
_computing_structure_solution    'olex2.solve 1.3-beta (Bourhis et al., 2015)'
_diffrn_ambient_temperature      298(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix3000
_diffrn_measured_fraction_theta_full 0.9872
_diffrn_measured_fraction_theta_max 0.9817
_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 97.00 142.00 0.50 0.78 -- 96.35 130.00 69.00 90
 2 \w 94.00 159.00 0.50 0.78 -- 96.35 33.00 -90.00 130
 3 \w 88.00 114.00 0.50 0.78 -- 96.35 136.00-136.00 52
 4 \w 100.00 143.00 0.50 0.78 -- 96.35 133.00-153.00 86
 5 \w 131.00 156.00 0.50 0.78 -- 96.35 136.00-136.00 50
 6 \w -42.00 -17.00 0.50 0.78 -- -82.50 42.00-120.00 50
 7 \w -31.00 -5.00 0.50 0.78 -- -82.50 5.00 3.00 52
 8 \w 8.00 34.00 0.50 0.20 -- -40.58 12.00 30.00 52
 9 \w -23.00 4.00 0.50 0.20 -- -40.58 12.00 30.00 54
 10 \w -23.00 9.00 0.50 0.20 -- 40.58 -12.00-150.00 64
 11 \w 92.00 118.00 0.50 0.78 -- 96.35-134.00 -22.00 52
 12 \w 10.00 55.00 0.50 0.20 -- 40.58 -50.00 120.00 90
 13 \w -19.00 6.00 0.50 0.20 -- 40.58 -50.00 120.00 50
 14 \w 46.00 87.00 0.50 0.78 -- 96.35-145.00 90.00 82
 15 \w 94.00 127.00 0.50 0.78 -- 96.35-145.00 90.00 66
 16 \w 57.00 82.00 0.50 0.20 -- 40.58-130.00 -2.00 50
 17 \w 42.00 71.00 0.50 0.78 -- 96.35-134.00 -22.00 58
 18 \w 47.00 82.00 0.50 0.78 -- 96.35 -68.00 30.00 70
 19 \w 31.00 64.00 0.50 0.78 -- 96.35 -59.00 -30.00 66
 20 \w 30.00 55.00 0.50 0.78 -- 96.35 -50.00-150.00 50
 21 \w -137.00-111.00 0.50 0.78 -- -82.50-145.00 -93.00 52
 22 \w -104.00 -72.00 0.50 0.20 -- -40.58-142.00-155.00 64
 23 \w -152.00-124.00 0.50 0.78 -- -82.50 -87.00 150.00 56
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix3000'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0371022000
_diffrn_orient_matrix_UB_12      0.0603281000
_diffrn_orient_matrix_UB_13      0.0011378000
_diffrn_orient_matrix_UB_21      0.0481032000
_diffrn_orient_matrix_UB_22      -0.0080047000
_diffrn_orient_matrix_UB_23      -0.0181779000
_diffrn_orient_matrix_UB_31      -0.0032482000
_diffrn_orient_matrix_UB_32      0.0008447000
_diffrn_orient_matrix_UB_33      -0.2552920000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0237
_diffrn_reflns_av_unetI/netI     0.0257
_diffrn_reflns_Laue_measured_fraction_full 0.9872
_diffrn_reflns_Laue_measured_fraction_max 0.9817
_diffrn_reflns_limit_h_max       35
_diffrn_reflns_limit_h_min       -33
_diffrn_reflns_limit_k_max       34
_diffrn_reflns_limit_k_min       -30
_diffrn_reflns_limit_l_max       3
_diffrn_reflns_limit_l_min       -7
_diffrn_reflns_number            4224
_diffrn_reflns_point_group_measured_fraction_full 0.5632
_diffrn_reflns_point_group_measured_fraction_max 0.5597
_diffrn_reflns_theta_full        67.6840
_diffrn_reflns_theta_max         68.06
_diffrn_reflns_theta_min         3.02
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.791
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.20078
_exptl_absorpt_correction_type   multi-scan
_exptl_crystal_colour            'Pale yellow'
_exptl_crystal_density_diffrn    1.407
_exptl_crystal_description       Cubic
_exptl_crystal_F_000             1956.403
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: Acetonitrile'
_refine_diff_density_max         0.2931
_refine_diff_density_min         -0.1350
_refine_diff_density_rms         0.0329
_refine_ls_abs_structure_details
'Flack, H. D. (1983). Acta Cryst. A39, 876-881.'
_refine_ls_abs_structure_Flack   0.00(2)
_refine_ls_d_res_high            0.8311
_refine_ls_d_res_low             14.6165
_refine_ls_goodness_of_fit_ref   1.0765
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_constraints    29
_refine_ls_number_parameters     254
_refine_ls_number_reflns         2033
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.0765
_refine_ls_R_factor_all          0.0441
_refine_ls_R_factor_gt           0.0435
_refine_ls_shift/su_max          0.0084
_refine_ls_shift/su_mean         0.0002
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1018P)^2^+0.8039P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1260
_refine_ls_wR_factor_ref         0.1271
_reflns_Friedel_coverage         0.128
_reflns_limit_h_max              29
_reflns_limit_h_min              -29
_reflns_limit_k_max              30
_reflns_limit_k_min              -29
_reflns_limit_l_max              3
_reflns_limit_l_min              -7
_reflns_number_gt                1984
_reflns_number_total             2033
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            d2ob01258h3.cif
_cod_data_source_block           205_auto
_cod_original_cell_volume        4454.43(15)
_cod_original_sg_symbol_Hall     ' R 3'
_cod_original_sg_symbol_H-M      'R 3'
_cod_database_code               7158823
_reflns_odcompleteness_completeness 100.00
_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.a Ternary CH refined with riding coordinates:
 C13(H13), C12(H12)
2.b Secondary CH2 refined with riding coordinates:
 C11(H11a,H11b)
2.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C16(H16), C15(H15), C17(H17), C19(H19), C6(H6), C3(H3), C5(H5),
 C18(H18)
2.d Idealised Me refined as rotating group:
 C20(H20a,H20b,H20c)
;
_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 3.504
_oxdiff_exptl_absorpt_empirical_full_min 0.390