Development of a Terpene Feedstock-Based Oxidative Synthetic Approach to the Illicium Sesquiterpenes.
Hung, Kevin; Condakes, Matthew L.; Novaes, Luiz F. T.; Harwood, Stephen J.; Morikawa, Takahiro; Yang, Zhi; Maimone, Thomas J.; Journal of the American Chemical Society 141 (2019) 3083–3099; doi:10.1021/jacs.8b12247

data_4128464
_publ_section_title
;
 Development of a Terpene Feedstock-Based Oxidative Synthetic Approach to
 the Illicium Sesquiterpenes.
;
_journal_issue                   7
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              3083
_journal_page_last               3099
_journal_paper_doi               10.1021/jacs.8b12247
_journal_volume                  141
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C15 H23 N O4 S'
_chemical_formula_sum            'C15 H23 N O4 S'
_chemical_formula_weight         313.40
_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'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2018-04-19
_audit_creation_method
;
Olex2 1.2-ac3
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.42853(7)
_cell_length_b                   12.26292(11)
_cell_length_c                   16.19471(13)
_cell_measurement_reflns_used    15321
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      78.6100
_cell_measurement_theta_min      5.4670
_cell_volume                     1475.26(2)
_computing_cell_refinement       'CrysAlisPro 1.171.39.45f (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.45f (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.45f (Rigaku OD, 2018)'
_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      100(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            'Pilatus 200K'
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_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    -10.00  74.00   0.50    0.50    --    0.00  48.00 118.00  168
  2  \w   -172.00 -81.00   0.50    0.50    -- -100.00 -74.00 179.00  182
  3  \w    -83.00 -26.00   0.50    0.50    -- -100.00  48.00 118.00  114
  4  \w   -176.00 -84.00   0.50    0.50    -- -100.00-115.00 102.00  184
  5  \w   -119.00 -28.00   0.50    0.50    -- -100.00  74.00 -52.00  182
  6  \w   -174.00 -90.00   0.50    0.50    -- -100.00 -48.00 -29.00  168
  7  \w     32.00  77.00   0.50    0.50    --  106.00 -48.00 -29.00   90
  8  \w    -15.00  31.00   0.50    0.50    --    0.00 -99.00 -30.00   92
  9  \w    -15.00  31.00   0.50    0.50    --    0.00 -99.00 150.00   92
 10  \w    -15.00  31.00   0.50    0.50    --    0.00 -99.00 -60.00   92
 11  \w    -15.00  31.00   0.50    0.50    --    0.00 -99.00  60.00   92
 12  \w    -80.00 -25.00   0.50    0.50    -- -100.00  45.00 120.00  110
 13  \w    -80.00 -25.00   0.50    0.50    -- -100.00  45.00 -60.00  110
 14  \w    -80.00 -25.00   0.50    0.50    -- -100.00  45.00-120.00  110
 15  \w   -170.00 -86.00   0.50    0.50    -- -100.00 -61.00  30.00  168
 16  \w    -80.00 -25.00   0.50    0.50    -- -100.00  45.00-180.00  110
 17  \w    -49.00 -23.00   0.50    0.50    -- -100.00  30.00   0.00   52
 18  \w   -106.00 -23.00   0.50    0.50    -- -100.00  15.00 150.00  166
 19  \w    136.00 166.00   0.50    0.50    --  106.00  15.00 -60.00   60
 20  \w     99.00 126.00   0.50    0.50    --  106.00  15.00 -60.00   54
 21  \w     32.00 100.00   0.50    0.50    --  106.00-111.00 -90.00  136
 22  \w     33.00  97.00   0.50    0.50    --  106.00-111.00-120.00  128
 23  \w     31.00  56.00   0.50    0.50    --  106.00 -30.00-120.00   50
 24  \w     29.00  62.00   0.50    0.50    --  106.00 -30.00  60.00   66
 25  \w     63.00 111.00   0.50    0.50    --  106.00-111.00 -60.00   96
 26  \w     33.00  58.00   0.50    0.50    --  106.00-111.00 -60.00   50
 27  \w    102.00 155.00   0.50    0.50    --  106.00  30.00  90.00  106
 28  \w     29.00  62.00   0.50    0.50    --  106.00 -30.00-150.00   66
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'ROD, Synergy Custom DW system, Pilatus 200K'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1715109000
_diffrn_orient_matrix_UB_12      0.0459460000
_diffrn_orient_matrix_UB_13      0.0406199000
_diffrn_orient_matrix_UB_21      0.1117032000
_diffrn_orient_matrix_UB_22      0.0921733000
_diffrn_orient_matrix_UB_23      0.0393955000
_diffrn_orient_matrix_UB_31      -0.0335824000
_diffrn_orient_matrix_UB_32      0.0718938000
_diffrn_orient_matrix_UB_33      -0.0764743000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0300
_diffrn_reflns_av_unetI/netI     0.0151
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            16205
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.472
_diffrn_reflns_theta_min         5.463
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.094
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.90046
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.45f (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.411
_exptl_crystal_description       block
_exptl_crystal_F_000             672
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.222
_refine_diff_density_min         -0.349
_refine_diff_density_rms         0.043
_refine_ls_abs_structure_details
;
 Flack x determined using 1251 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.003(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.020
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     196
_refine_ls_number_reflns         3008
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.020
_refine_ls_R_factor_all          0.0264
_refine_ls_R_factor_gt           0.0263
_refine_ls_shift/su_max          0.006
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0393P)^2^+0.5981P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0700
_refine_ls_wR_factor_ref         0.0700
_reflns_Friedel_coverage         0.724
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.998
_reflns_number_gt                2999
_reflns_number_total             3008
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b12247_si_015.cif
_cod_data_source_block           mc004
_cod_original_cell_volume        1475.27(2)
_cod_database_code               4128464
_shelx_shelxl_version_number     2017/1
_chemical_oxdiff_formula         'C15 H21 O4 N1 S1'
_shelx_estimated_absorpt_t_max   0.850
_shelx_estimated_absorpt_t_min   0.679
_reflns_odcompleteness_completeness 99.66
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C9(H9), C13(H13), C2(H2), C14(H14)
2.b Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C7(H7A,H7B), C12(H12A,H12B), C10(H10A,H10B), C4(H4A,H4B), C3(H3A,
 H3B)
2.c Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C15(H15A,H15B,H15C)
;
_shelx_res_checksum              6365
_shelx_hkl_checksum              17278
_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 1.670
_oxdiff_exptl_absorpt_empirical_full_min 0.678