Regioselective Synthesis of 5-Metalated 2-Pyrones by Intramolecular Oxymetalation of Carbonyl-ene-yne Compounds Using Indium Trihalide.
Yata, Tetsuji; Kita, Yuji; Nishimoto, Yoshihiro; Yasuda, Makoto; The Journal of organic chemistry 84 (2019) 14330–14341; doi:10.1021/acs.joc.9b02186

data_4033623
_publ_section_title
;
 Regioselective Synthesis of 5-Metalated 2-Pyrones by Intramolecular
 Oxymetalation of Carbonyl-ene-yne Compounds Using Indium Trihalide.
;
_journal_issue                   21
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              14330
_journal_page_last               14341
_journal_paper_doi               10.1021/acs.joc.9b02186
_journal_volume                  84
_journal_year                    2019
_chemical_formula_moiety         'C31 H22 O3'
_chemical_formula_sum            'C31 H22 O3'
_chemical_formula_weight         442.48
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-05-11
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 100.540(7)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   10.4592(8)
_cell_length_b                   8.1844(6)
_cell_length_c                   13.6348(10)
_cell_measurement_reflns_used    5040
_cell_measurement_temperature    123
_cell_measurement_theta_max      27.5060
_cell_measurement_theta_min      2.7210
_cell_volume                     1147.48(15)
_computing_cell_refinement       'CrysAlisPro 1.171.39.31d (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.31d (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.31d (Rigaku OD, 2017)'
_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_temperature      123
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.805
_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    -19.00  66.00   0.50    2.92    --   -5.34  15.00  -7.00  170
  2  \w    -25.00  25.00   0.50    2.92    --   -5.34 -99.00 120.00  100
  3  \w    -24.00  10.00   0.50    2.92    --   -5.34 -99.00 -30.00   68
  4  \w    -26.00  29.00   0.50    2.92    --    5.49 -99.00-150.00  110
  5  \w    -74.00  -8.00   0.50    2.92    --   -5.34 -15.00-177.00  132
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'XtaLAB Synergy, Single source at offset/far, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0241733000
_diffrn_orient_matrix_UB_12      0.0007332000
_diffrn_orient_matrix_UB_13      0.0453412000
_diffrn_orient_matrix_UB_21      0.0633514000
_diffrn_orient_matrix_UB_22      0.0175169000
_diffrn_orient_matrix_UB_23      0.0266138000
_diffrn_orient_matrix_UB_31      -0.0128487000
_diffrn_orient_matrix_UB_32      0.0848313000
_diffrn_orient_matrix_UB_33      -0.0059368000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0317
_diffrn_reflns_av_unetI/netI     0.0405
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.805
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            11855
_diffrn_reflns_point_group_measured_fraction_full 0.954
_diffrn_reflns_point_group_measured_fraction_max 0.733
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.656
_diffrn_reflns_theta_min         1.981
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.082
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.84710
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.31d (Rigaku Oxford Diffraction, 2017)
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    1.281
_exptl_crystal_description       prism
_exptl_crystal_F_000             464
_exptl_crystal_size_max          0.08
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.117
_refine_diff_density_min         -0.229
_refine_diff_density_rms         0.040
_refine_ls_abs_structure_details
;
 Flack x determined using 1511 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.3(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.052
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     308
_refine_ls_number_reflns         5201
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.051
_refine_ls_R_factor_all          0.0556
_refine_ls_R_factor_gt           0.0430
_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^)+(0.0496P)^2^+0.0296P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0967
_refine_ls_wR_factor_ref         0.1042
_reflns_Friedel_coverage         0.714
_reflns_Friedel_fraction_full    0.900
_reflns_Friedel_fraction_max     0.652
_reflns_number_gt                4213
_reflns_number_total             5201
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo9b02186_si_002.cif
_cod_data_source_block           7m
_cod_depositor_comments
'Adding full bibliography for 4033619--4033624.cif.'
_cod_database_code               4033623
_shelx_shelxl_version_number     2017/1
_chemical_oxdiff_formula         'C31 H22 O3'
_reflns_odcompleteness_completeness 99.76
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Aromatic/amide H refined with riding coordinates:
 C12(H12), C8(H8), C14(H14), C17(H17), C29(H29), C18(H18), C10(H10), C33(H33),
 C11(H11), C16(H16), C9(H9), C20(H20), C24(H24), C32(H32), C15(H15), C30(H30),
 C23(H23), C22(H22), C21(H21)
2.b Idealised Me refined as rotating group:
 C34(H34a,H34b,H34c)
;
_shelx_res_checksum              17841
_shelx_hkl_checksum              97592
_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 1.279
_oxdiff_exptl_absorpt_empirical_full_min 0.754