Synthesis of 6-Substituted 2-Pyrones Starting from Renewable Resources: Total Synthesis of Sibirinone, (E)-6-(Pent-1-en-1-yl)-2H-pyran-2-one, and (E)-6-(Hept-1-en-1-yl)-2H-pyran-2-one.
Dobler, Daniel; Reiser, Oliver; The Journal of organic chemistry 81 (2016) 10357–10365; doi:10.1021/acs.joc.6b01339

data_4037040
_publ_section_title
;
 Synthesis of 6-Substituted 2-Pyrones Starting from Renewable Resources:
 Total Synthesis of Sibirinone, (E)-6-(Pent-1-en-1-yl)-2H-pyran-2-one, and
 (E)-6-(Hept-1-en-1-yl)-2H-pyran-2-one.
;
_journal_issue                   21
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              10357
_journal_page_last               10365
_journal_paper_doi               10.1021/acs.joc.6b01339
_journal_volume                  81
_journal_year                    2016
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C14 H11 N O6'
_chemical_formula_sum            'C14 H11 N O6'
_chemical_formula_weight         289.24
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2016-05-02
_audit_creation_method
;
Olex2 1.2-alpha
(compiled 2016.02.24 svn.r3266 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                90
_cell_angle_beta                 100.939(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   4.25027(12)
_cell_length_b                   29.6140(5)
_cell_length_c                   10.3858(2)
_cell_measurement_reflns_used    10709
_cell_measurement_temperature    123.01(10)
_cell_measurement_theta_max      73.4310
_cell_measurement_theta_min      4.5660
_cell_volume                     1283.48(5)
_computing_cell_refinement       'CrysAlisPro 1.171.38.42b (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.42b (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.42b (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      123.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.1773
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.985
_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    -38.00  74.00   1.00    4.00    --   40.71 -77.00 -30.00  112
  2  \w     14.00 117.00   1.00    4.00    --   40.71  37.00-120.00  103
  3  \w     11.00 115.00   1.00    4.00    --   40.71  57.00 120.00  104
  4  \w     77.00 158.00   1.00   17.50    --  106.98  61.00  90.00   81
  5  \w     23.00 109.00   1.00   17.50    --  106.98 -94.00 -60.00   86
  6  \w     29.00  69.00   1.00   17.50    --  106.98 -30.00  60.00   40
  7  \w     29.00  69.00   1.00   17.50    --  106.98 -30.00  30.00   40
  8  \w     23.00 109.00   1.00   17.50    --  106.98 -94.00  30.00   86
  9  \w     73.00 158.00   1.00   17.50    --  106.98 125.00  30.00   85
 10  \w     77.00 158.00   1.00   17.50    --  106.98  61.00 120.00   81
 11  \w     29.00  69.00   1.00   17.50    --  106.98 -30.00  90.00   40
 12  \w     29.00  69.00   1.00   17.50    --  106.98 -30.00 -30.00   40
 13  \w     29.00  69.00   1.00   17.50    --  106.98 -30.00   0.00   40
 14  \w     32.00  77.00   1.00   17.50    --  106.98 -45.00 -90.00   45
 15  \w     29.00  69.00   1.00   17.50    --  106.98 -30.00 -60.00   40
 16  \w     28.00 141.00   1.00   17.50    --  106.98 -77.00  60.00  113
 17  \w     23.00 109.00   1.00   17.50    --  106.98 -94.00-180.00   86
 18  \w    -33.00  70.00   1.00    4.00    --   40.71 -57.00  90.00  103
 19  \w      7.00 119.00   1.00    4.00    --   40.71  77.00-120.00  112
 20  \w     11.00 115.00   1.00    4.00    --   40.71  57.00   0.00  104
 21  \w    -33.00  70.00   1.00    4.00    --   40.71 -57.00-150.00  103
 22  \w     77.00 130.00   1.00   17.50    --  106.98  61.00 150.00   53
 23  \w     77.00 158.00   1.00   17.50    --  106.98  61.00-180.00   81
 24  \w     46.00 158.00   1.00   17.50    --  106.98  15.00 -60.00  112
 25  \w     73.00 158.00   1.00   17.50    --  106.98  77.00  30.00   85
 26  \w     76.00 158.00   1.00   17.50    --  106.98  30.00  30.00   82
 27  \w     73.00 158.00   1.00   17.50    --  106.98  77.00 -90.00   85
 28  \w     79.00 158.00   1.00   17.50    --  106.98  45.00 -30.00   79
 29  \w     29.00  69.00   1.00   17.50    --  106.98 -30.00 150.00   40
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Single source at offset, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1753196000
_diffrn_orient_matrix_UB_12      -0.0162720000
_diffrn_orient_matrix_UB_13      -0.1083194000
_diffrn_orient_matrix_UB_21      -0.0353118000
_diffrn_orient_matrix_UB_22      -0.0492987000
_diffrn_orient_matrix_UB_23      0.0424440000
_diffrn_orient_matrix_UB_31      -0.3228531000
_diffrn_orient_matrix_UB_32      -0.0034349000
_diffrn_orient_matrix_UB_33      -0.0963322000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0322
_diffrn_reflns_av_unetI/netI     0.0291
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       5
_diffrn_reflns_limit_h_min       -5
_diffrn_reflns_limit_k_max       36
_diffrn_reflns_limit_k_min       -36
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            16728
_diffrn_reflns_point_group_measured_fraction_full 0.990
_diffrn_reflns_point_group_measured_fraction_max 0.965
_diffrn_reflns_theta_full        67.500
_diffrn_reflns_theta_max         73.606
_diffrn_reflns_theta_min         4.336
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.017
_exptl_absorpt_correction_T_max  0.980
_exptl_absorpt_correction_T_min  0.943
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.42b (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    1.497
_exptl_crystal_description       irregular
_exptl_crystal_F_000             600
_exptl_crystal_recrystallization_method
'The material was recrystallised from --- by'
_exptl_crystal_size_max          0.218
_exptl_crystal_size_mid          0.094
_exptl_crystal_size_min          0.052
_refine_diff_density_max         0.216
_refine_diff_density_min         -0.213
_refine_diff_density_rms         0.051
_refine_ls_abs_structure_details
;
 Flack x determined using 2207 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.02(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.065
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     381
_refine_ls_number_reflns         4990
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.065
_refine_ls_R_factor_all          0.0376
_refine_ls_R_factor_gt           0.0361
_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^)+(0.0662P)^2^+0.1185P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0966
_refine_ls_wR_factor_ref         0.0983
_reflns_Friedel_coverage         0.921
_reflns_Friedel_fraction_full    0.982
_reflns_Friedel_fraction_max     0.944
_reflns_number_gt                4811
_reflns_number_total             4990
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo6b01339_si_005.cif
_cod_data_source_block           ap_nc_gauss
_cod_original_cell_volume        1283.49(5)
_cod_database_code               4037040
_chemical_oxdiff_formula         'C14 h11 N O6'
_chemical_oxdiff_usercomment     'Dobler_AK Reiser_DD455'
_reflns_odcompleteness_completeness 99.66
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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 Ternary CH refined with riding coordinates:
 C21(H21), C34(H34)
2.b Aromatic/amide H refined with riding coordinates:
 C14(H14), C19(H19), C22(H22), C23(H23), C26(H26), C27(H27), C28(H28),
 C30(H30), C31(H31), C33(H33), C36(H36), C40(H40), C41(H41), C42(H42)
2.c Idealised Me refined as rotating group:
 C35(H35A,H35B,H35C), C39(H39A,H39B,H39C)
;
_shelx_res_checksum              59163
_shelx_hkl_checksum              36370
_shelx_shelxl_version_number     2014/7
_olex2_date_sample_data_collection 2016-05-26
_olex2_date_sample_submission    2016-04-25
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems CryoStream 700'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a Lindemann tube with inert oil'
_olex2_submission_original_sample_id 'DD 455'
_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 1.480
_oxdiff_exptl_absorpt_empirical_full_min 0.646