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_4128473
_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 H22 O3'
_chemical_formula_sum            'C15 H22 O3'
_chemical_formula_weight         250.32
_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     dual
_audit_creation_date             2018-03-13
_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                 96.3190(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.38830(10)
_cell_length_b                   11.55480(10)
_cell_length_c                   13.55300(10)
_cell_measurement_reflns_used    26537
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      78.5320
_cell_measurement_theta_min      3.7840
_cell_volume                     1305.65(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 0.995
_diffrn_measured_fraction_theta_max 0.981
_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    -16.00  70.00   0.50    0.50    --    0.00  67.00   8.00  172
  2  \w   -116.00 -30.00   0.50    0.50    -- -100.00  67.00   8.00  172
  3  \w   -170.00 -84.00   0.50    0.50    -- -100.00 -67.00-125.00  172
  4  \w     90.00 176.00   0.50    0.50    --  106.00  67.00   8.00  172
  5  \w    -15.00  31.00   0.50    0.50    --    0.00 -99.00   0.00   92
  6  \w    -45.00  20.00   0.50    0.50    --    0.00 -77.00 150.00  130
  7  \w    -15.00  31.00   0.50    0.50    --    0.00 -99.00-150.00   92
  8  \w    -15.00  31.00   0.50    0.50    --    0.00 -99.00  90.00   92
  9  \w     -7.00  77.00   0.50    0.50    --    0.00  38.00 150.00  168
 10  \w    -70.00  16.00   0.50    0.50    --    0.00 -67.00-125.00  172
 11  \w    -15.00  31.00   0.50    0.50    --    0.00 -99.00 -60.00   92
 12  \w   -177.00 -94.00   0.50    0.50    -- -100.00 -30.00 -90.00  166
 13  \w    -80.00 -25.00   0.50    0.50    -- -100.00  45.00-150.00  110
 14  \w   -172.00 -80.00   0.50    0.50    -- -100.00 -77.00 150.00  184
 15  \w   -175.00 -91.00   0.50    0.50    -- -100.00 -45.00 120.00  168
 16  \w   -120.00 -28.00   0.50    0.50    -- -100.00  77.00  30.00  184
 17  \w   -175.00 -91.00   0.50    0.50    -- -100.00 -45.00-180.00  168
 18  \w   -170.00 -86.00   0.50    0.50    -- -100.00 -61.00 150.00  168
 19  \w   -107.00 -21.00   0.50    0.50    -- -100.00  15.00 150.00  172
 20  \w   -178.00 -93.00   0.50    0.50    -- -100.00 -15.00 120.00  170
 21  \w   -177.00 -94.00   0.50    0.50    -- -100.00 -30.00  90.00  166
 22  \w    -72.00 -23.00   0.50    0.50    -- -100.00  30.00   0.00   98
 23  \w   -114.00 -30.00   0.50    0.50    -- -100.00  61.00-180.00  168
 24  \w   -177.00 -94.00   0.50    0.50    -- -100.00 -30.00  60.00  166
 25  \w   -175.00 -91.00   0.50    0.50    -- -100.00 -45.00  90.00  168
 26  \w    -80.00 -25.00   0.50    0.50    -- -100.00  45.00   0.00  110
 27  \w    -80.00 -25.00   0.50    0.50    -- -100.00  45.00 150.00  110
 28  \w   -177.00 -92.00   0.50    0.50    -- -100.00   0.00 -90.00  170
 29  \w     92.00 176.00   0.50    0.50    --  106.00  61.00   0.00  168
 30  \w     86.00 178.00   0.50    0.50    --  106.00  77.00  30.00  184
 31  \w    100.00 169.00   0.50    0.50    --  106.00  30.00   0.00  138
 32  \w     38.00  74.00   0.50    0.50    --  106.00 -45.00-120.00   72
 33  \w     83.00 126.00   0.50    0.50    --  106.00 -77.00 150.00   86
 34  \w     47.00  74.00   0.50    0.50    --  106.00 -77.00 150.00   54
 35  \w     99.00 133.00   0.50    0.50    --  106.00  15.00 150.00   68
 36  \w    100.00 170.00   0.50    0.50    --  106.00  30.00 -30.00  140
 37  \w     74.00  99.00   0.50    0.50    --  106.00 -94.00 -60.00   50
 38  \w     30.00  55.00   0.50    0.50    --  106.00 -94.00 -60.00   50
 39  \w    101.00 174.00   0.50    0.50    --  106.00  61.00 120.00  146
 40  \w    150.00 176.00   0.50    0.50    --  106.00  30.00 -60.00   52
 41  \w    100.00 147.00   0.50    0.50    --  106.00  30.00 -60.00   94
 42  \w     67.00  97.00   0.50    0.50    --  106.00 -94.00 -90.00   60
 43  \w     31.00  61.00   0.50    0.50    --  106.00 -94.00 -90.00   60
 44  \w    149.00 176.00   0.50    0.50    --  106.00  61.00  60.00   54
 45  \w     31.00  71.00   0.50    0.50    --  106.00 -45.00  90.00   80
 46  \w     47.00  73.00   0.50    0.50    --  106.00 -45.00-180.00   52
 47  \w    108.00 143.00   0.50    0.50    --  106.00  61.00  60.00   70
 48  \w     61.00 109.00   0.50    0.50    --  106.00 -94.00-120.00   96
 49  \w     30.00  72.00   0.50    0.50    --  106.00 -94.00  60.00   84
 50  \w     60.00  86.00   0.50    0.50    --  106.00 -67.00-125.00   52
;
_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      -0.1656114000
_diffrn_orient_matrix_UB_12      -0.0527509000
_diffrn_orient_matrix_UB_13      0.0114548000
_diffrn_orient_matrix_UB_21      -0.0230144000
_diffrn_orient_matrix_UB_22      0.0877227000
_diffrn_orient_matrix_UB_23      0.0829177000
_diffrn_orient_matrix_UB_31      -0.0787036000
_diffrn_orient_matrix_UB_32      0.0854220000
_diffrn_orient_matrix_UB_33      -0.0779134000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0295
_diffrn_reflns_av_unetI/netI     0.0144
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.981
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            28219
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.972
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         78.947
_diffrn_reflns_theta_min         3.281
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.697
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.84895
_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    1.273
_exptl_crystal_description       block
_exptl_crystal_F_000             544
_exptl_crystal_size_max          0.28
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.185
_refine_diff_density_min         -0.155
_refine_diff_density_rms         0.034
_refine_ls_abs_structure_details
;
 Flack x determined using 2547 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.08(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.055
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     331
_refine_ls_number_reflns         5484
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.054
_refine_ls_R_factor_all          0.0286
_refine_ls_R_factor_gt           0.0285
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0382P)^2^+0.3009P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0745
_refine_ls_wR_factor_ref         0.0745
_reflns_Friedel_coverage         0.886
_reflns_Friedel_fraction_full    0.994
_reflns_Friedel_fraction_max     0.962
_reflns_number_gt                5468
_reflns_number_total             5484
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b12247_si_012.cif
_cod_data_source_block           kh_146_2_2_3
_cod_database_code               4128473
_shelx_shelxl_version_number     2017/1
_chemical_oxdiff_formula         'C15 O4 H22'
_shelx_estimated_absorpt_t_max   0.873
_shelx_estimated_absorpt_t_min   0.829
_reflns_odcompleteness_completeness 99.54
_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:
 C26(H26), C14(H14), C11(H11), C2(H2), C17(H17), C29(H29)
2.b Secondary CH2 refined with riding coordinates:
 C4(H4A,H4B), C6(H6A,H6B), C27(H27A,H27B), C19(H19A,H19B), C8(H8A,H8B),
 C23(H23A,H23B), C28(H28A,H28B), C21(H21A,H21B), C12(H12A,H12B), C13(H13A,H13B)
2.c Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C15(H15A,H15B,H15C), C16(H16A,H16B,H16C), C30(H30A,H30B,
 H30C), C10(H10A,H10B,H10C), C25(H25A,H25B,H25C)
;
_shelx_res_checksum              87795
_shelx_hkl_checksum              36418
_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 1.722
_oxdiff_exptl_absorpt_empirical_full_min 0.722