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_7158824
_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_formula_moiety         '3(C23 H23 N O4 S2), C22.537 H23 N O4 S2'
_chemical_formula_sum            'C91.537 H92 N4 O16 S8'
_chemical_formula_weight         1766.302
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_Int_Tables_number      2
_atom_sites_solution_primary     iterative
_audit_creation_date             2021-07-15
_audit_creation_method
;
Olex2 1.3-beta
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_audit_update_record
;
2021-07-26 deposited with the CCDC.	2022-08-03 downloaded from the CCDC.
;
_cell_angle_alpha                88.0358(9)
_cell_angle_beta                 84.5699(10)
_cell_angle_gamma                88.8661(10)
_cell_formula_units_Z            2
_cell_length_a                   14.9969(2)
_cell_length_b                   15.45226(17)
_cell_length_c                   19.0015(2)
_cell_measurement_reflns_used    33004
_cell_measurement_temperature    298(2)
_cell_measurement_theta_max      68.0140
_cell_measurement_theta_min      2.3950
_cell_volume                     4380.39(9)
_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      300(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix3000
_diffrn_measured_fraction_theta_full 0.9956
_diffrn_measured_fraction_theta_max 0.9906
_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     12.00  68.00   0.50    0.20    --   40.58 -77.00 -60.00  112
  2  \w    -26.00  -1.00   0.50    0.20    --   40.58 -77.00 -60.00   50
  3  \w     27.00 101.00   0.50    0.20    --   40.58  50.00  60.00  148
  4  \w     75.00 101.00   0.50    0.20    --   40.58  44.00 108.00   52
  5  \w     33.00  67.00   0.50    0.20    --   40.58  44.00 108.00   68
  6  \w     11.00  39.00   0.50    0.20    --   40.58 -38.00  90.00   56
  7  \w    -25.00   3.00   0.50    0.20    --   40.58 -38.00  90.00   56
  8  \w    -19.00  24.00   0.50    0.20    --   40.58 -38.00  60.00   86
  9  \w     18.00  63.00   0.50    0.20    --   40.58 -64.00-150.00   90
 10  \w    -25.00   0.00   0.50    0.20    --   40.58 -64.00-150.00   50
 11  \w    -21.00  31.00   0.50    0.20    --   40.58 -25.00-150.00  104
 12  \w      4.00  30.00   0.50    0.20    --   40.58 -44.00 -42.00   52
 13  \w     58.00 102.00   0.50    0.66    --   96.35 -77.00  90.00   88
 14  \w     30.00  68.00   0.50    0.66    --   96.35 -59.00 150.00   76
 15  \w     46.00  74.00   0.50    0.66    --   96.35 -68.00 120.00   56
 16  \w     30.00  61.00   0.50    0.66    --   96.35 -59.00  60.00   62
 17  \w     29.00  82.00   0.50    0.66    --   96.35 -68.00  30.00  106
 18  \w     31.00  57.00   0.50    0.66    --   96.35 -50.00  90.00   52
 19  \w     32.00  68.00   0.50    0.66    --   96.35 -59.00 -30.00   72
 20  \w     30.00  55.00   0.50    0.66    --   96.35 -50.00 -60.00   50
 21  \w     30.00  55.00   0.50    0.66    --   96.35 -50.00-120.00   50
 22  \w     31.00  57.00   0.50    0.66    --   96.35 -50.00-180.00   52
 23  \w     30.00  55.00   0.50    0.66    --   96.35 -50.00 120.00   50
 24  \w     69.00 108.00   0.50    0.66    --   96.35-117.00  90.00   78
 25  \w     60.00 110.00   0.50    0.66    --   96.35-117.00 150.00  100
 26  \w     43.00 108.00   0.50    0.66    --   96.35-117.00  60.00  130
 27  \w     22.00  82.00   0.50    0.66    --   96.35 -96.00 -30.00  120
 28  \w     36.00 110.00   0.50    0.66    --   96.35-117.00 -30.00  148
 29  \w     56.00  83.00   0.50    0.66    --   96.35 -96.00 -90.00   54
 30  \w     52.00 110.00   0.50    0.66    --   96.35-117.00 -90.00  116
 31  \w     57.00 106.00   0.50    0.66    --   96.35-117.00-120.00   98
 32  \w     27.00  53.00   0.50    0.66    --   96.35 -96.00 -90.00   52
 33  \w     18.00  77.00   0.50    0.20    --   40.58-104.00 -60.00  118
 34  \w     40.00  65.00   0.50    0.66    --   96.35 -87.00   0.00   50
 35  \w     31.00  90.00   0.50    0.66    --   96.35 -87.00 -30.00  118
 36  \w    102.00 127.00   0.50    0.66    --   96.35 -87.00   0.00   50
 37  \w     81.00 142.00   0.50    0.66    --   96.35  25.00-180.00  122
 38  \w     73.00 162.00   0.50    0.66    --   96.35  68.00  30.00  178
 39  \w     89.00 164.00   0.50    0.66    --   96.35  59.00  60.00  150
 40  \w     78.00 156.00   0.50    0.66    --   96.35  50.00  90.00  156
 41  \w    129.00 164.00   0.50    0.66    --   96.35  44.00 108.00   70
 42  \w     92.00 124.00   0.50    0.66    --   96.35  44.00 108.00   64
 43  \w     76.00 115.00   0.50    0.66    --   96.35  59.00 120.00   78
 44  \w    128.00 164.00   0.50    0.66    --   96.35  59.00 120.00   72
 45  \w     84.00 134.00   0.50    0.66    --   96.35  33.00  30.00  100
 46  \w    126.00 152.00   0.50    0.66    --   96.35  96.00 120.00   52
 47  \w    120.00 157.00   0.50    0.66    --   96.35 117.00  30.00   74
 48  \w    137.00 164.00   0.50    0.66    --   96.35 145.00 -60.00   54
 49  \w     85.00 122.00   0.50    0.66    --   96.35 145.00 -60.00   74
 50  \w    102.00 130.00   0.50    0.66    --   96.35 117.00 -60.00   56
 51  \w    101.00 136.00   0.50    0.66    --   96.35 117.00 -30.00   70
 52  \w    111.00 154.00   0.50    0.66    --   96.35  96.00   0.00   86
 53  \w    -89.00 -19.00   0.50    0.20    --  -40.58 138.00  60.00  140
 54  \w    -63.00 -37.00   0.50    0.66    --  -82.50 117.00  30.00   52
 55  \w    -53.00 -20.00   0.50    0.20    --  -40.58 138.00 -60.00   66
 56  \w    -96.00 -62.00   0.50    0.20    --  -40.58 138.00 -60.00   68
 57  \w    -79.00 -15.00   0.50    0.66    --  -82.50  77.00 -90.00  128
 58  \w    -63.00 -37.00   0.50    0.66    --  -82.50  59.00-180.00   52
 59  \w    -47.00 -22.00   0.50    0.66    --  -82.50  42.00-150.00   50
 60  \w    -42.00 -15.00   0.50    0.66    --  -82.50  42.00-120.00   54
 61  \w    -44.00 -16.00   0.50    0.66    --  -82.50  42.00   0.00   56
 62  \w    -50.00 -15.00   0.50    0.66    --  -82.50  44.00 108.00   70
 63  \w    -35.00   0.00   0.50    0.20    --  -40.58  44.00 108.00   70
 64  \w    -27.00  30.00   0.50    0.20    --  -40.58  25.00 -60.00  114
 65  \w    -29.00  12.00   0.50    0.20    --  -40.58  25.00 -90.00   82
 66  \w    -24.00  28.00   0.50    0.20    --  -40.58  12.00-120.00  104
 67  \w    -22.00  34.00   0.50    0.20    --  -40.58  12.00-150.00  112
 68  \w   -100.00 -57.00   0.50    0.20    --  -40.58 -77.00-120.00   86
 69  \w    -93.00 -67.00   0.50    0.66    --  -82.50 -44.00 -42.00   52
 70  \w   -141.00-115.00   0.50    0.66    --  -82.50 -44.00 -42.00   52
 71  \w    -88.00 -27.00   0.50    0.20    --  -40.58 -44.00 -42.00  122
;
_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      0.0131588000
_diffrn_orient_matrix_UB_12      0.0855528000
_diffrn_orient_matrix_UB_13      0.0367302000
_diffrn_orient_matrix_UB_21      0.0885616000
_diffrn_orient_matrix_UB_22      -0.0359056000
_diffrn_orient_matrix_UB_23      0.0251659000
_diffrn_orient_matrix_UB_31      0.0513269000
_diffrn_orient_matrix_UB_32      0.0366834000
_diffrn_orient_matrix_UB_33      -0.0682443000
_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  0.0386
_diffrn_reflns_av_unetI/netI     0.0362
_diffrn_reflns_Laue_measured_fraction_full 0.9956
_diffrn_reflns_Laue_measured_fraction_max 0.9906
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            46312
_diffrn_reflns_point_group_measured_fraction_full 0.9956
_diffrn_reflns_point_group_measured_fraction_max 0.9906
_diffrn_reflns_theta_full        67.6840
_diffrn_reflns_theta_max         68.06
_diffrn_reflns_theta_min         2.86
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.450
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.03842
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.96a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'PALE YELLOW'
_exptl_crystal_density_diffrn    1.339
_exptl_crystal_description       cubic
_exptl_crystal_F_000             1866.765
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: Acetonitrile'
_exptl_crystal_size_max          0.212
_exptl_crystal_size_mid          0.201
_exptl_crystal_size_min          0.198
_refine_diff_density_max         1.2546
_refine_diff_density_min         -1.1463
_refine_diff_density_rms         0.0957
_refine_ls_d_res_high            0.8311
_refine_ls_d_res_low             15.4410
_refine_ls_goodness_of_fit_ref   1.0169
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_constraints    145
_refine_ls_number_parameters     1118
_refine_ls_number_reflns         15812
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.0169
_refine_ls_R_factor_all          0.0783
_refine_ls_R_factor_gt           0.0679
_refine_ls_shift/su_max          0.0005
_refine_ls_shift/su_mean         0.0013
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0950P)^2^+4.3691P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1748
_refine_ls_wR_factor_ref         0.1821
_reflns_Friedel_coverage         0.0
_reflns_limit_h_max              18
_reflns_limit_h_min              -17
_reflns_limit_k_max              18
_reflns_limit_k_min              -18
_reflns_limit_l_max              22
_reflns_limit_l_min              0
_reflns_number_gt                13223
_reflns_number_total             15812
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            d2ob01258h3.cif
_cod_data_source_block           331_auto
_cod_original_cell_volume        4380.40(9)
_cod_database_code               7158824
_reflns_odcompleteness_completeness 99.80
_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. Others
 Sof(S2b)=Sof(H2b)=1-FVAR(1)
 Sof(C15)=Sof(S2a)=FVAR(1)
3.a Ternary CH refined with riding coordinates:
 C90(H90), C83(H83), C46(H46), C14(H14), C37(H37), C58(H58), C23(H23), C57(H57)
3.b Secondary CH2 refined with riding coordinates:
 C82(H82a,H82b), C36(H36a,H36b), C59(H59a,H59b), C13(H13a,H13b)
3.c Aromatic/amide H refined with riding coordinates:
 C71(H71), C29(H29), C2(H2), C25(H25), C75(H75), C45(H45), C41(H41), C18(H18),
 C22(H22), C42(H42), C19(H19), C44(H44), C43(H43), C20(H20), C21(H21), C89(H89),
  C68(H68), C65(H65), C85(H85), C87(H87), C6(H6), C86(H86), C66(H66), C52(H52),
 C88(H88), C48(H48), C67(H67), C64(H64)
3.d Idealised Me refined as rotating group:
 C76(H76a,H76b,H76c), C77(H77a,H77b,H77c), C9(H9a,H9b,H9c), C78(H78a,H78b,
 H78c), C54(H54a,H54b,H54c), C55(H55a,H55b,H55c), C31(H31a,H31b,H31c), C7(H7a,
 H7b,H7c), C91(H91a,H91b,H91c), C38(H38a,H38b,H38c), C30(H30a,H30b,H30c),
 C8(H8a,H8b,H8c), C32(H32a,H32b,H32c), C53(H53a,H53b,H53c), C61(H61a,H61b,H61c)
;
_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 16.326
_oxdiff_exptl_absorpt_empirical_full_min 0.578