First enantioselective synthesis of gingesulfonic acids and unequivocal determination of their absolute stereochemistry.
Bencivenni, Grazia; Moccia, Maria; Ravelli, Andrea; Gillick-Healy, Malachi W; Kelly, Brian G.; Adamo, Mauro F. A.; Organic & biomolecular chemistry 18 (2020) 1091–1094; doi:10.1039/c9ob02662b

data_7157329
_publ_section_title
;
 First enantioselective synthesis of gingesulfonic acids and unequivocal
 determination of their absolute stereochemistry.
;
_journal_issue                   6
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              1091
_journal_page_last               1094
_journal_paper_doi               10.1039/c9ob02662b
_journal_volume                  18
_journal_year                    2020
_chemical_formula_moiety         'C18 H28 Na O7 S, C H4 O'
_chemical_formula_sum            'C19 H32 Na O8 S'
_chemical_formula_weight         443.49
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2016-02-19
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_audit_update_record
;
2019-10-08 deposited with the CCDC.	2020-01-24 downloaded from the CCDC.
;
_cell_angle_alpha                88.598(8)
_cell_angle_beta                 88.036(6)
_cell_angle_gamma                82.569(7)
_cell_formula_units_Z            2
_cell_length_a                   4.8228(4)
_cell_length_b                   15.0261(16)
_cell_length_c                   15.5936(15)
_cell_measurement_reflns_used    4176
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      68.33
_cell_measurement_theta_min      2.84
_cell_volume                     1119.66(19)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_collection       'APEX 3 (Bruker, 2015) '
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_computing_molecular_graphics    'XP (Bruker, 2008-2014)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.0
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.987
_diffrn_measured_fraction_theta_max 0.984
_diffrn_measurement_device       'DUO Kappa diffractometer'
_diffrn_measurement_device_type  'Bruker SMART APEX2 area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0769
_diffrn_reflns_av_unetI/netI     0.0907
_diffrn_reflns_Laue_measured_fraction_full 0.987
_diffrn_reflns_Laue_measured_fraction_max 0.984
_diffrn_reflns_limit_h_max       5
_diffrn_reflns_limit_h_min       -5
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            12214
_diffrn_reflns_point_group_measured_fraction_full 0.987
_diffrn_reflns_point_group_measured_fraction_max 0.984
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         68.288
_diffrn_reflns_theta_min         2.836
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.835
_exptl_absorpt_correction_T_max  0.7531
_exptl_absorpt_correction_T_min  0.6021
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.1252 before and 0.0896 after correction.
The Ratio of minimum to maximum transmission is 0.7995.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.315
_exptl_crystal_description       irregular
_exptl_crystal_F_000             474
_exptl_crystal_recrystallization_method 'MeOH crystallization'
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.893
_refine_diff_density_min         -0.579
_refine_diff_density_rms         0.132
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.094
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     277
_refine_ls_number_reflns         4041
_refine_ls_number_restraints     28
_refine_ls_restrained_S_all      1.093
_refine_ls_R_factor_all          0.1298
_refine_ls_R_factor_gt           0.1107
_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^)+(0.1122P)^2^+6.7122P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2990
_refine_ls_wR_factor_ref         0.3125
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3026
_reflns_number_total             4041
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9ob02662b2.cif
_cod_data_source_block           tcd409
_cod_depositor_comments          'Adding full bibliography for 7157329.cif.'
_cod_database_code               7157329
_shelx_estimated_absorpt_t_max   0.930
_shelx_estimated_absorpt_t_min   0.838
_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, All O(H) groups
2. Restrained distances
 O24-H24
 0.87 with sigma of 0.01
 C2S-O2S
 1.4 with sigma of 0.02
 C25-H24
 1.895249 with sigma of 0.02
 Na1-H24
 3.108011 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(O1S) \\sim Ueq, Uanis(C1S) \\sim Ueq, Uanis(C2S) \\sim Ueq, Uanis(O2S)
\\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(O2S) = Uanis(O1S)
Uanis(C2S) = Uanis(C1S)
4. Others
 Sof(O2S)=Sof(H2S)=Sof(C2S)=Sof(H2SA)=Sof(H2SB)=Sof(H2SC)=1-FVAR(1)
 Sof(O1S)=Sof(H1S)=Sof(C1S)=Sof(H1SA)=Sof(H1SB)=Sof(H1SC)=FVAR(1)
5.a Everything fixed:
 H1S, H2S
5.b Ternary CH refined with riding coordinates:
 C15(H15)
5.c Secondary CH2 refined with riding coordinates:
 C10(H10A,H10B), C11(H11A,H11B), C14(H14A,H14B), C16(H16A,H16B), C17(H17A,
 H17B), C18(H18A,H18B), C19(H19A,H19B)
5.d Aromatic/amide H refined with riding coordinates:
 C1(H1), C4(H4), C5(H5)
5.e Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C20(H20A,H20B,H20C), C25(H25A,H25B,H25C), C1S(H1SA,H1SB,
 H1SC), C2S(H2SA,H2SB,H2SC)
;
_shelx_res_checksum              51772
_shelx_shelxl_version_number     2014/7
_olex2_exptl_crystal_mounting_method 'Mitegen loop'
_olex2_submission_original_sample_id AR82
_olex2_submission_special_instructions 'No special instructions were received'