Continuous-Flow Preparation of γ-Butyrolactone Scaffolds from Renewable Fumaric and Itaconic Acids under Photosensitized Conditions
Gérardy, Romaric; Winter, Marc; Horn, Clemens R.; Vizza, Alessandra; Van Hecke, Kristof; Monbaliu, Jean-Christophe M.; Organic Process Research & Development 21 (2017) 2012–; doi:10.1021/acs.oprd.7b00314

data_1548361
_publ_section_title
;
 Continuous-Flow Preparation of \g-Butyrolactone Scaffolds from Renewable
 Fumaric and Itaconic Acids under Photosensitized Conditions
;
_journal_issue                   12
_journal_name_full               'Organic Process Research &amp; Development'
_journal_page_first              2012
_journal_paper_doi               10.1021/acs.oprd.7b00314
_journal_volume                  21
_journal_year                    2017
_chemical_formula_moiety         'C8 H12 O4'
_chemical_formula_sum            'C8 H12 O4'
_chemical_formula_weight         172.18
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2017-05-01
_audit_creation_method
;
Olex2 1.2
(compiled Mar 28 2017 19:26:29 for OlexSys, GUI svn.r5335)
;
_cell_angle_alpha                90
_cell_angle_beta                 92.826(9)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   5.3618(6)
_cell_length_b                   15.150(2)
_cell_length_c                   10.5728(11)
_cell_measurement_reflns_used    3473
_cell_measurement_temperature    100.0(1)
_cell_measurement_theta_max      74.1060
_cell_measurement_theta_min      5.0170
_cell_volume                     857.80(17)
_computing_cell_refinement       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.41 (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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.0(1)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4839
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.956
_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    -91.00   7.00   1.00    2.00    --  -41.80 114.00 -98.00   98
  2  \w   -131.00 -36.00   1.00    2.00    --  -41.80-177.00  33.00   95
  3  \w     57.00 151.00   1.00    6.00    --  109.13 177.00  38.00   94
  4  \w     33.00 117.00   1.00    6.00    --  109.13-114.00 170.00   84
  5  \w     55.00 156.00   1.00    6.00    --  109.13-177.00  33.00  101
  6  \w    100.00 178.00   1.00    6.00    --  109.13 114.00 -98.00   78
  7  \w   -114.00 -14.00   1.00    2.00    --  -41.80 -57.00  60.00  100
  8  \w      1.00  83.00   1.00    2.00    --   41.80 -99.00  90.00   82
  9  \w     23.00  98.00   1.00    2.00    --   41.80-125.00-120.00   75
 10  \w     33.00 137.00   1.00    6.00    --  109.13 -30.00 -30.00  104
 11  \w     26.00 109.00   1.00    6.00    --  109.13 -94.00-180.00   83
 12  \w     26.00 109.00   1.00    6.00    --  109.13 -94.00   0.00   83
 13  \w     33.00 137.00   1.00    6.00    --  109.13 -30.00 120.00  104
 14  \w   -114.00 -14.00   1.00    2.00    --  -41.80 -57.00-150.00  100
 15  \w   -118.00  -9.00   1.00    2.00    --  -41.80 -77.00-180.00  109
 16  \w   -114.00 -14.00   1.00    2.00    --  -41.80 -57.00 -30.00  100
 17  \w     81.00 140.00   1.00    6.00    --  109.13  30.00 -30.00   59
 18  \w     81.00 178.00   1.00    6.00    --  109.13  30.00 150.00   97
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0667549000
_diffrn_orient_matrix_UB_12      0.0812838000
_diffrn_orient_matrix_UB_13      0.0790655000
_diffrn_orient_matrix_UB_21      0.1620697000
_diffrn_orient_matrix_UB_22      0.0584346000
_diffrn_orient_matrix_UB_23      -0.0823944000
_diffrn_orient_matrix_UB_31      -0.2281087000
_diffrn_orient_matrix_UB_32      0.0177767000
_diffrn_orient_matrix_UB_33      -0.0908229000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0445
_diffrn_reflns_av_unetI/netI     0.0288
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.956
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            7976
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.956
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.314
_diffrn_reflns_theta_min         5.105
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.906
_exptl_absorpt_correction_T_max  0.959
_exptl_absorpt_correction_T_min  0.918
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.41 (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 colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.333
_exptl_crystal_description       block
_exptl_crystal_F_000             368
_exptl_crystal_size_max          0.176
_exptl_crystal_size_mid          0.098
_exptl_crystal_size_min          0.078
_refine_diff_density_max         0.700
_refine_diff_density_min         -0.477
_refine_diff_density_rms         0.072
_refine_ls_extinction_coef       0.0025(8)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     SHELXL
_refine_ls_goodness_of_fit_ref   1.099
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     120
_refine_ls_number_reflns         1745
_refine_ls_number_restraints     9
_refine_ls_restrained_S_all      1.117
_refine_ls_R_factor_all          0.0990
_refine_ls_R_factor_gt           0.0756
_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^)+(0.0544P)^2^+1.6187P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1691
_refine_ls_wR_factor_ref         0.1956
_reflns_Friedel_coverage         0.000
_reflns_number_gt                1337
_reflns_number_total             1745
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            op7b00314_si_002.cif
_cod_data_source_block           jcm001
_cod_depositor_comments          'Adding full bibliography for 1548361.cif.'
_cod_database_code               1548361
_shelxl_version_number           2013-4
_chemical_oxdiff_formula         'C8 H12 O4'
_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, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
2. Restrained distances
 C1-C4B
 1.52 with sigma of 0.02
 C3A-C4A
 1.53 with sigma of 0.01
 C3B-C4B
 1.53 with sigma of 0.01
 C3A-C2
 1.51 with sigma of 0.01
 C3B-C2
 1.51 with sigma of 0.01
 C4A-C5
 1.54 with sigma of 0.01
 C4B-C5
 1.54 with sigma of 0.01
 C4A-C2
 2.39 with sigma of 0.02
 C4B-C2
 2.39 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C3A) = Uanis(C3B)
Uanis(C4A) = Uanis(C4B)
4. Others
 Sof(C3B)=Sof(H3BA)=Sof(H3BB)=Sof(C4B)=Sof(H4B)=Sof(H5BC)=Sof(H5BD)=1-FVAR(1)
 Sof(C3A)=Sof(H3AA)=Sof(H3AB)=Sof(C4A)=Sof(H4A)=Sof(H5AA)=Sof(H5AB)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C4A(H4A), C4B(H4B)
5.b Secondary CH2 refined with riding coordinates:
 C3A(H3AA,H3AB), C3B(H3BA,H3BB), C5(H5AA,H5AB), C5(H5BC,H5BD)
5.c Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C8(H8A,H8B,H8C)
5.d Idealised tetrahedral OH refined as rotating group:
 O4(H4)
;
_shelx_res_checksum              12742
_shelx_hkl_checksum              86671
_olex2_exptl_crystal_mounting_method 'mounted on a nylon loop'
_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 1.368
_oxdiff_exptl_absorpt_empirical_full_min 0.785