Asymmetric total synthesis of humulane sesquiterpenoids alashanoids B, C, E, and F and 2,9-humuladien-6-ol-8-one.
Barik, Rasmita; Nanda, Samik; Organic & biomolecular chemistry 22 (2024) 4478–4487; doi:10.1039/d4ob00393d

data_7159891
_publ_section_title
;
 Asymmetric total synthesis of humulane sesquiterpenoids alashanoids B, C,
 E, and F and 2,9-humuladien-6-ol-8-one.
;
_journal_issue                   22
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              4478
_journal_page_last               4487
_journal_paper_doi               10.1039/d4ob00393d
_journal_volume                  22
_journal_year                    2024
_chemical_formula_moiety         'C16 H26 O3'
_chemical_formula_sum            'C16 H26 O3'
_chemical_formula_weight         266.37
_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             2023-10-13
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2019.04.23 svn.r3594 for Rigaku Oxford Diffraction, GUI svn.r5739)
;
_audit_update_record
;
2023-11-05 deposited with the CCDC.	2024-04-04 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 107.436(14)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.7763(12)
_cell_length_b                   14.2275(14)
_cell_length_c                   12.0706(16)
_cell_measurement_reflns_used    6201
_cell_measurement_temperature    297.6(6)
_cell_measurement_theta_max      31.2050
_cell_measurement_theta_min      2.1710
_cell_volume                     1601.8(4)
_computing_cell_refinement       'CrysAlisPro 1.171.41.95a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.95a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.95a (Rigaku OD, 2021)'
_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_environment      air
_diffrn_ambient_temperature      297.6(6)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.823
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \f    -10.27 348.73   1.00    5.00  73.22 -17.64  31.50    --   359
  2  \w    -67.13  -0.13   1.00    5.00    --  -17.64  94.56 145.16   67
  3  \w    -67.13  -0.13   1.00    5.00    --  -17.64  94.56   1.16   67
  4  \w    -67.13  -0.13   1.00    5.00    --  -17.64  94.56-142.84   67
  5  \w   -113.30  10.70   1.00    5.00    --  -17.64 -59.25 173.08  124
  6  \w   -113.30  10.70   1.00    5.00    --  -17.64 -59.25 -33.92  124
  7  \w    -67.13  -0.13   1.00    5.00    --  -17.64  94.56  73.16   67
  8  \f   -339.92  19.08   1.00    5.00  11.45 -17.64 -59.25    --   359
  9  \w    -75.95   0.05   1.00    5.00    --  -26.47  94.56 -34.84   76
 10  \w   -113.30  10.70   1.00    5.00    --  -17.64 -59.25  71.08  124
 11  \w    -58.31  -0.31   1.00    5.00    --   -8.82  94.56 -34.84   58
 12  \f   -349.73   9.27   1.00    5.00   4.74 -17.64 -31.50    --   359
;
_diffrn_measurement_device       'abstract diffractometer'
_diffrn_measurement_device_type
'Saxi-CrysAlisPro-abstract goniometer imported SAXI images'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0211410000
_diffrn_orient_matrix_UB_12      -0.0400541000
_diffrn_orient_matrix_UB_13      -0.0361062000
_diffrn_orient_matrix_UB_21      -0.0723464000
_diffrn_orient_matrix_UB_22      0.0151237000
_diffrn_orient_matrix_UB_23      -0.0151937000
_diffrn_orient_matrix_UB_31      0.0097171000
_diffrn_orient_matrix_UB_32      0.0255598000
_diffrn_orient_matrix_UB_33      -0.0475555000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.2346
_diffrn_reflns_av_unetI/netI     0.2864
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.823
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            110246
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.781
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         38.284
_diffrn_reflns_theta_min         1.768
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.074
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.34508
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.95a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_density_diffrn    1.105
_exptl_crystal_F_000             584
_refine_diff_density_max         0.549
_refine_diff_density_min         -0.238
_refine_diff_density_rms         0.095
_refine_ls_abs_structure_details
;
 Flack x determined using 1023 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -1.7(10)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.994
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     353
_refine_ls_number_reflns         13876
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      0.994
_refine_ls_R_factor_all          0.4427
_refine_ls_R_factor_gt           0.1640
_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^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3375
_refine_ls_wR_factor_ref         0.4664
_reflns_Friedel_coverage         0.843
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.737
_reflns_number_gt                3620
_reflns_number_total             13876
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4ob00393d2.cif
_cod_data_source_block           sn_rb_r1673_pj_13oct
_cod_depositor_comments
'Adding full bibliography for 7159890--7159891.cif.'
_cod_original_cell_volume        1601.8(3)
_cod_database_code               7159891
_shelx_shelxl_version_number     2018/3
_reflns_odcompleteness_completeness 82.29
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     38.19
_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:
 C00C(H00V), C00E(H00E), C00G(H00G), C00J(H00J), C00K(H00Y), C00N(H00)
2.b Secondary CH2 refined with riding coordinates:
 C00D(H00W,H00X), C00O(H00A,H00B), C00P(H1,H), C00Q(H00C,H00D), C00R(H2,HA),
 C00Y(H00S,H00T)
2.c Aromatic/amide H refined with riding coordinates:
 C00A(H00U), C00F(H00F), C00I(H00I), C00L(H00Z)
2.d Idealised Me refined as rotating group:
 C00S(H00H,H00K,H00L), C00T(H3,HB,HC), C00U(H00M,H00N,H00O), C00V(H4,HD,HE),
 C00W(H5,HF,HG), C00X(H00P,H00Q,H00R), C00Z(H6,HH,HI), C010(H01A,H01B,H01C),
 C011(H01D,H01E,H01F), C012(H01G,H01H,H01I)
;
_shelx_res_checksum              67327
_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 1.636
_oxdiff_exptl_absorpt_empirical_full_min 0.412