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_7230740
_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         'C15 H14 O3'
_chemical_formula_sum            'C15 H14 O3'
_chemical_formula_weight         242.26
_space_group_crystal_system      hexagonal
_space_group_IT_number           170
_space_group_name_Hall           'P 65'
_space_group_name_H-M_alt        'P 65'
_symmetry_space_group_name_Hall  'P 65'
_symmetry_space_group_name_H-M   'P 65'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2017-05-03
_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                120
_cell_formula_units_Z            24
_cell_length_a                   13.5583(2)
_cell_length_b                   13.5583(2)
_cell_length_c                   45.7998(6)
_cell_measurement_reflns_used    42176
_cell_measurement_temperature    110.05(10)
_cell_measurement_theta_max      71.0440
_cell_measurement_theta_min      3.7450
_cell_volume                     7291.30(18)
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (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
;
Superflip (Palatinus & Chapuis, 2007;Palatinus & van der Lee, 2008;
Palatinus et al., 2012)
;
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      110.05(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 -90.00   90
  3  \w     75.00 124.00   1.00    4.00    --   54.00 156.00  89.00   49
  4  \w    -15.00  75.00   1.00    4.00    --   54.00 -57.00-120.00   90
  5  \w     23.00 111.00   1.00    4.00    --   54.00-125.00  90.00   88
  6  \w     33.00 123.00   1.00    4.00    --   54.00  57.00 150.00   90
  7  \w     33.00 123.00   1.00    4.00    --   54.00  57.00 -60.00   90
  8  \w    -15.00  75.00   1.00    4.00    --   54.00 -57.00 150.00   90
  9  \w     33.00 123.00   1.00    4.00    --   54.00  57.00  30.00   90
 10  \w     86.00 176.00   1.00    8.00    --  108.00  63.00  30.00   90
 11  \w     86.00 176.00   1.00    8.00    --  108.00  63.00 -90.00   90
 12  \w    100.00 178.00   1.00    8.00    --  108.00 111.00 120.00   78
 13  \w     36.00 116.00   1.00    8.00    --  108.00-111.00  60.00   80
 14  \w     86.00 178.00   1.00    8.00    --  108.00  50.00  90.00   92
 15  \w     86.00 176.00   1.00    8.00    --  108.00  63.00 -30.00   90
 16  \w     86.00 178.00   1.00    8.00    --  108.00  50.00-150.00   92
 17  \w     86.00 178.00   1.00    8.00    --  108.00  50.00 -60.00   92
 18  \w     78.00 178.00   1.00    8.00    --  108.00  77.00-120.00  100
 19  \w     38.00 130.00   1.00    8.00    --  108.00 -50.00-120.00   92
 20  \w    -54.00   3.00   1.00    1.00    --    0.00 119.00 -66.00   57
 21  \w    -69.00  21.00   1.00    1.00    --    0.00 -57.00  30.00   90
 22  \w     24.00 124.00   1.00    4.00    --   54.00  77.00 -30.00  100
 23  \w    -18.00  80.00   1.00    4.00    --   54.00 -37.00   0.00   98
 24  \w     33.00 123.00   1.00    4.00    --   54.00  57.00  90.00   90
 25  \w     24.00 124.00   1.00    4.00    --   54.00  77.00-150.00  100
 26  \w     36.00 116.00   1.00    8.00    --  108.00-111.00-120.00   80
 27  \w     86.00 139.00   1.00    8.00    --  108.00  50.00-180.00   53
 28  \w     36.00 116.00   1.00    8.00    --  108.00-111.00 -60.00   80
 29  \w     86.00 178.00   1.00    8.00    --  108.00  50.00 120.00   92
 30  \w     78.00 178.00   1.00    8.00    --  108.00  77.00   0.00  100
 31  \w     38.00 138.00   1.00    8.00    --  108.00 -77.00  60.00  100
 32  \w     74.00 178.00   1.00    8.00    --  108.00  25.00-180.00  104
;
_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      -0.0411218000
_diffrn_orient_matrix_UB_12      0.0004753000
_diffrn_orient_matrix_UB_13      0.0313234000
_diffrn_orient_matrix_UB_21      -0.1234490000
_diffrn_orient_matrix_UB_22      -0.0534799000
_diffrn_orient_matrix_UB_23      -0.0111709000
_diffrn_orient_matrix_UB_31      -0.0168746000
_diffrn_orient_matrix_UB_32      -0.1198076000
_diffrn_orient_matrix_UB_33      0.0050207000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.1146
_diffrn_reflns_av_unetI/netI     0.0425
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       54
_diffrn_reflns_limit_l_min       -54
_diffrn_reflns_number            86742
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        67.056
_diffrn_reflns_theta_max         67.056
_diffrn_reflns_theta_min         3.765
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.747
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.481
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (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 yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.324
_exptl_crystal_description       needle
_exptl_crystal_F_000             3072
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: ethanol'
_exptl_crystal_size_max          0.287
_exptl_crystal_size_mid          0.142
_exptl_crystal_size_min          0.088
_refine_diff_density_max         0.593
_refine_diff_density_min         -0.473
_refine_diff_density_rms         0.095
_refine_ls_abs_structure_details
;
 Flack x determined using 3928 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.06(10)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.072
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     602
_refine_ls_number_reflns         8674
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.072
_refine_ls_R_factor_all          0.0914
_refine_ls_R_factor_gt           0.0909
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0978P)^2^+26.2792P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2298
_refine_ls_wR_factor_ref         0.2302
_reflns_Friedel_coverage         0.973
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     1.000
_reflns_number_gt                8577
_reflns_number_total             8674
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8gc01227j2.cif
_cod_data_source_block           jhc1711
_cod_depositor_comments
'Adding full bibliography for 7230738--7230745.cif.'
_cod_original_cell_volume        7291.3(2)
_cod_database_code               7230740
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C15 H14 O3'
_chemical_oxdiff_usercomment     'Liam lmhtranscinnamaldehyde from MeOH'
_reflns_odcompleteness_completeness 99.91
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.669(5)
 0.331(5)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
3. Uiso/Uaniso restraints and constraints
Uanis(C51) = Uanis(C36)
Uanis(C52) = Uanis(C37)
Uanis(C49) = Uanis(C34)
Uanis(C44) = Uanis(C59)
Uanis(C43) = Uanis(C58)
Uanis(C19) = Uanis(C4)
Uanis(C17) = Uanis(C2)
Uanis(C31) = Uanis(C46)
4.a Ternary CH refined with riding coordinates:
 C2(H2), C4(H4), C17(H17), C19(H19), C32(H32), C34(H34), C47(H47), C49(H49)
4.b Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C5(H5A,H5B), C18(H18A,H18B), C20(H20A,H20B), C33(H33A,H33B),
 C35(H35A,H35B), C48(H48A,H48B), C50(H50A,H50B)
4.c Aromatic/amide H refined with riding coordinates:
 C7(H7), C8(H8), C9(H9), C11(H11), C12(H12), C13(H13), C14(H14), C15(H15),
 C22(H22), C23(H23), C24(H24), C26(H26), C27(H27), C28(H28), C29(H29), C30(H30),
  C37(H37), C38(H38), C39(H39), C41(H41), C42(H42), C43(H43), C44(H44),
 C45(H45), C52(H52), C53(H53), C54(H54), C56(H56), C57(H57), C58(H58), C59(H59),
  C60(H60)
;
_shelx_res_checksum              37810
_olex2_date_sample_data_collection 2017-04-28
_olex2_date_sample_submission    2017-04-05
_olex2_exptl_crystal_mounting_method 'oil on 200 micrometre micromount'
_olex2_submission_original_sample_id lmhTranscinnamaldehyde
_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 1.172
_oxdiff_exptl_absorpt_empirical_full_min 0.825