Development of pharmaceutically relevant bio-based intermediates though aldol condensation and Claisen–Schmidt reactions of dihydrolevoglucosenone (Cyrene®)
Hughes, Liam; McElroy, Con R.; Whitwood, Adrian C.; Hunt, Andrew J.; Green Chemistry 20 (2018) 4423–; doi:10.1039/C8GC01227J

data_7230741
_publ_section_title
;
 Development of pharmaceutically relevant bio-based intermediates though
 aldol condensation and Claisen--Schmidt reactions of
 dihydrolevoglucosenone (Cyrene&#x00AE;)
;
_journal_issue                   19
_journal_name_full               'Green Chemistry'
_journal_page_first              4423
_journal_paper_doi               10.1039/C8GC01227J
_journal_volume                  20
_journal_year                    2018
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C11 H10 O3 S'
_chemical_formula_sum            'C11 H10 O3 S'
_chemical_formula_weight         222.25
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2017-04-10
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5335)
;
_audit_update_record
;
2018-04-17 deposited with the CCDC.
2018-05-25 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   6.32713(7)
_cell_length_b                   10.32552(10)
_cell_length_c                   15.23806(18)
_cell_measurement_reflns_used    6187
_cell_measurement_temperature    110.00(10)
_cell_measurement_theta_max      70.9670
_cell_measurement_theta_min      4.3050
_cell_volume                     995.516(19)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43 (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      N~2~
_diffrn_ambient_temperature      110.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.1450
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_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    -69.00  21.00   1.00    1.00    --    0.00 -57.00-150.00   90
  2  \w    -69.00  21.00   1.00    1.00    --    0.00 -57.00  60.00   90
  3  \w    -18.00  80.00   1.00    1.00    --   54.00 -37.00 120.00   98
  4  \w     23.00 111.00   1.00    1.00    --   54.00-125.00  30.00   88
  5  \w     33.00 123.00   1.00    1.00    --   54.00  57.00 -60.00   90
  6  \w     33.00 123.00   1.00    1.00    --   54.00  57.00  60.00   90
  7  \w    101.00 178.00   1.00    1.00    --  108.00  95.00  -3.00   77
  8  \w     40.00 130.00   1.00    1.00    --  108.00 -63.00-120.00   90
  9  \w     86.00 178.00   1.00    1.00    --  108.00  50.00  30.00   92
 10  \w     38.00 138.00   1.00    1.00    --  108.00 -77.00  30.00  100
 11  \w    100.00 178.00   1.00    1.00    --  108.00 111.00 -60.00   78
 12  \w     35.00 142.00   1.00    1.00    --  108.00 -25.00  30.00  107
 13  \w    -70.00  30.00   1.00    1.00    --    0.00 -77.00 -30.00  100
 14  \w     33.00 123.00   1.00    1.00    --   54.00  55.00 128.00   90
 15  \w    -15.00  75.00   1.00    1.00    --   54.00 -57.00  60.00   90
 16  \w     33.00 123.00   1.00    1.00    --   54.00  57.00-150.00   90
 17  \w     82.00 178.00   1.00    1.00    --  108.00  37.00  90.00   96
 18  \w     74.00 178.00   1.00    1.00    --  108.00  25.00 -60.00  104
 19  \w     36.00 178.00   1.00    1.00    --  108.00  12.00-150.00  142
 20  \w     78.00 178.00   1.00    1.00    --  108.00  77.00-150.00  100
 21  \w     36.00 116.00   1.00    1.00    --  108.00-111.00-120.00   80
 22  \w    -40.00  25.00   1.00    1.00    --    0.00  95.00  -3.00   65
 23  \w    -15.00  28.00   1.00    1.00    --   54.00 -57.00 -90.00   43
 24  \w     33.00 123.00   1.00    1.00    --   54.00  57.00   0.00   90
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0873594000
_diffrn_orient_matrix_UB_12      -0.0736489000
_diffrn_orient_matrix_UB_13      0.0800555000
_diffrn_orient_matrix_UB_21      0.1359965000
_diffrn_orient_matrix_UB_22      0.1183648000
_diffrn_orient_matrix_UB_23      0.0243513000
_diffrn_orient_matrix_UB_31      -0.1821533000
_diffrn_orient_matrix_UB_32      0.0531947000
_diffrn_orient_matrix_UB_33      0.0566916000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0170
_diffrn_reflns_av_unetI/netI     0.0111
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            8921
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        66.871
_diffrn_reflns_theta_max         66.871
_diffrn_reflns_theta_min         5.174
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.763
_exptl_absorpt_correction_T_max  0.716
_exptl_absorpt_correction_T_min  0.604
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015)
Numerical absorption correction based on gaussian integration over
            a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.483
_exptl_crystal_description       irregular
_exptl_crystal_F_000             464
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: acetonitrile'
_exptl_crystal_size_max          0.293
_exptl_crystal_size_mid          0.245
_exptl_crystal_size_min          0.189
_refine_diff_density_max         0.197
_refine_diff_density_min         -0.181
_refine_diff_density_rms         0.037
_refine_ls_abs_structure_details
;
 Flack x determined using 708 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.014(5)
_refine_ls_extinction_coef       0.0021(5)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2014/7 (Sheldrick 2014'
_refine_ls_goodness_of_fit_ref   1.046
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     137
_refine_ls_number_reflns         1777
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.046
_refine_ls_R_factor_all          0.0210
_refine_ls_R_factor_gt           0.0209
_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^)+(0.0343P)^2^+0.2764P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0563
_refine_ls_wR_factor_ref         0.0563
_reflns_Friedel_coverage         0.680
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     1.000
_reflns_number_gt                1766
_reflns_number_total             1777
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8gc01227j2.cif
_cod_data_source_block           jhc1702
_cod_depositor_comments
'Adding full bibliography for 7230738--7230745.cif.'
_cod_original_cell_volume        995.516(18)
_cod_database_code               7230741
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C11 H10 O3 S'
_chemical_oxdiff_usercomment     'Liam lmh2-thiophene'
_reflns_odcompleteness_completeness 99.91
_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
2.a Ternary CH refined with riding coordinates:
 C2(H2), C4(H4)
2.b Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C5(H5A,H5B)
2.c Aromatic/amide H refined with riding coordinates:
 C7(H7), C9(H9), C10(H10), C11(H11)
;
_olex2_date_sample_data_collection 2017-04-05
_olex2_date_sample_submission    2017-04-05
_olex2_exptl_crystal_mounting_method 'oil on 100 micrometre micromount'
_olex2_submission_original_sample_id lmh2-thiophene
_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 1.260
_oxdiff_exptl_absorpt_empirical_full_min 0.871