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_4128472
_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 H24 O3'
_chemical_formula_sum            'C15 H24 O3'
_chemical_formula_weight         252.34
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2018-03-06
_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                 90.872(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   8.7529(2)
_cell_length_b                   6.37230(10)
_cell_length_c                   11.9743(2)
_cell_measurement_reflns_used    11013
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      78.4100
_cell_measurement_theta_min      5.0290
_cell_volume                     667.80(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 1.000
_diffrn_measured_fraction_theta_max 0.989
_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   -111.00 -24.00   0.50    0.50    -- -100.00 102.00 -63.00  174
  2  \w   -176.00 -89.00   0.50    0.50    -- -100.00-102.00-166.00  174
  3  \w     30.00 111.00   0.50    0.50    --  106.00-102.00-166.00  162
  4  \w     83.00 178.00   0.50    0.50    --  106.00 102.00 -63.00  190
  5  \w    -15.00  31.00   0.50    0.50    --    0.00 -99.00  30.00   92
  6  \w    -15.00  31.00   0.50    0.50    --    0.00 -99.00 120.00   92
  7  \w    -15.00  31.00   0.50    0.50    --    0.00 -99.00-180.00   92
  8  \w    -15.00  31.00   0.50    0.50    --    0.00 -99.00   0.00   92
  9  \w    -20.00  45.00   0.50    0.50    --    0.00  77.00 -30.00  130
 10  \w    -20.00  45.00   0.50    0.50    --    0.00  77.00  90.00  130
 11  \w    -15.00  31.00   0.50    0.50    --    0.00 -99.00 -60.00   92
 12  \w   -176.00 -86.00   0.50    0.50    -- -100.00-111.00 -30.00  180
 13  \w   -169.00 -84.00   0.50    0.50    -- -100.00 -65.00 121.04  170
 14  \w    -72.00 -23.00   0.50    0.50    -- -100.00  30.00 -90.00   98
 15  \w   -120.00 -28.00   0.50    0.50    -- -100.00  77.00 -60.00  184
 16  \w   -175.00 -91.00   0.50    0.50    -- -100.00 -45.00-174.89  168
 17  \w   -112.00 -24.00   0.50    0.50    -- -100.00 111.00 120.00  176
 18  \w   -158.00 -43.00   0.50    0.50    -- -100.00 179.00 -60.00  230
 19  \w   -112.00 -24.00   0.50    0.50    -- -100.00 111.00 -60.00  176
 20  \w    -80.00 -25.00   0.50    0.50    -- -100.00  45.00 -90.00  110
 21  \w    -80.00 -25.00   0.50    0.50    -- -100.00  45.00 150.00  110
 22  \w   -158.00 -43.00   0.50    0.50    -- -100.00 179.00  60.00  230
 23  \w   -171.00 -87.00   0.50    0.50    -- -100.00 -58.00  98.69  168
 24  \w   -158.00 -43.00   0.50    0.50    -- -100.00 179.00-180.00  230
 25  \w     99.00 178.00   0.50    0.50    --  106.00  15.00  30.00  158
 26  \w     36.00 120.00   0.50    0.50    --  106.00 -61.00-180.00  168
 27  \w     29.00  66.00   0.50    0.50    --  106.00 -30.00 150.00   74
 28  \w     30.00 112.00   0.50    0.50    --  106.00-111.00-180.00  164
 29  \w     29.00 114.00   0.50    0.50    --  106.00   0.00   0.00  170
 30  \w     30.00 112.00   0.50    0.50    --  106.00-111.00  90.00  164
 31  \w     92.00 176.00   0.50    0.50    --  106.00  61.00  90.00  168
 32  \w     34.00 126.00   0.50    0.50    --  106.00 -77.00 -30.00  184
 33  \w     30.00 109.00   0.50    0.50    --  106.00 -94.00  90.00  158
 34  \w     34.00 126.00   0.50    0.50    --  106.00 -77.00-150.00  184
 35  \w     30.00 109.00   0.50    0.50    --  106.00 -94.00 -60.00  158
 36  \w     29.00  66.00   0.50    0.50    --  106.00 -30.00-120.00   74
 37  \w    -79.00   6.00   0.50    0.50    --    0.00 -19.00  30.00  170
 38  \w     -7.00  77.00   0.50    0.50    --    0.00  38.00  30.00  168
 39  \w    -77.00   8.00   0.50    0.50    --    0.00   0.00-150.00  170
 40  \w    -45.00  20.00   0.50    0.50    --    0.00 -77.00 150.00  130
 41  \w    -13.00  72.00   0.50    0.50    --    0.00  57.00-180.00  170
;
_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      0.1602365000
_diffrn_orient_matrix_UB_12      -0.0997304000
_diffrn_orient_matrix_UB_13      -0.0018582000
_diffrn_orient_matrix_UB_21      -0.0671484000
_diffrn_orient_matrix_UB_22      -0.2091677000
_diffrn_orient_matrix_UB_23      0.0412696000
_diffrn_orient_matrix_UB_31      -0.0279430000
_diffrn_orient_matrix_UB_32      -0.0691132000
_diffrn_orient_matrix_UB_33      -0.1218704000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0426
_diffrn_reflns_av_unetI/netI     0.0255
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.989
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            14264
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.971
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         79.004
_diffrn_reflns_theta_min         3.692
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.682
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.91475
_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    1.255
_exptl_crystal_description       block
_exptl_crystal_F_000             276
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.165
_refine_diff_density_min         -0.229
_refine_diff_density_rms         0.039
_refine_ls_abs_structure_details
;
 Flack x determined using 1161 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.02(9)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.091
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     173
_refine_ls_number_reflns         2801
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.091
_refine_ls_R_factor_all          0.0335
_refine_ls_R_factor_gt           0.0320
_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^)+(0.0376P)^2^+0.1723P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0816
_refine_ls_wR_factor_ref         0.0826
_reflns_Friedel_coverage         0.797
_reflns_Friedel_fraction_full    0.996
_reflns_Friedel_fraction_max     0.949
_reflns_number_gt                2694
_reflns_number_total             2801
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b12247_si_014.cif
_cod_data_source_block           kh_9_014_2
_cod_database_code               4128472
_shelx_shelxl_version_number     2017/1
_chemical_oxdiff_formula         'C15 O3 H24'
_shelx_estimated_absorpt_t_max   0.967
_shelx_estimated_absorpt_t_min   0.935
_reflns_odcompleteness_completeness 100.00
_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:
 C8(H8), C11(H11), C9(H9), C2(H2A)
2.b Secondary CH2 refined with riding coordinates:
 C14(H14A,H14B), C4(H4A,H4B), C15(H15A,H15B), C7(H7A,H7B), C12(H12A,H12B),
 C3(H3A,H3B)
2.c Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C), C1(H1A,H1B,H1C)
;
_shelx_res_checksum              81888
_shelx_hkl_checksum              34907
_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 1.481
_oxdiff_exptl_absorpt_empirical_full_min 0.676