Enantioselective Approach to (-)-Hamigeran B and (-)-4-Bromohamigeran B via Catalytic Asymmetric Hydrogenation of Racemic Ketone To Assemble the Chiral Core Framework.
Lin, Han; Xiao, Li-Jun; Zhou, Min-Jie; Yu, Hong-Ming; Xie, Jian-Hua; Zhou, Qi-Lin; Organic letters 18 (2016) 1434–1437; doi:10.1021/acs.orglett.6b00369

data_1555500
_publ_section_title
;
 Enantioselective Approach to (-)-Hamigeran B and (-)-4-Bromohamigeran B
 via Catalytic Asymmetric Hydrogenation of Racemic Ketone To Assemble the
 Chiral Core Framework.
;
_journal_issue                   6
_journal_name_full               'Organic letters'
_journal_page_first              1434
_journal_page_last               1437
_journal_paper_doi               10.1021/acs.orglett.6b00369
_journal_volume                  18
_journal_year                    2016
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C19 H26 O3'
_chemical_formula_sum            'C19 H26 O3'
_chemical_formula_weight         302.40
_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   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2015-12-23
_audit_creation_method
;
Olex2 1.2-ac21
(compiled 2015.09.16 svn.r134, GUI svn.r4998)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   6.43415(9)
_cell_length_b                   13.96950(20)
_cell_length_c                   18.8234(2)
_cell_measurement_reflns_used    12018
_cell_measurement_temperature    173(2)
_cell_measurement_theta_max      78.7310
_cell_measurement_theta_min      3.9430
_cell_volume                     1691.88(4)
_computing_cell_refinement       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_collection       'CrystalClear-SM Expert 2.1 b42 (Rigaku, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      173.15
_diffrn_detector                 PILT
_diffrn_detector_area_resol_mean 5.814
_diffrn_measured_fraction_theta_full 1.000
_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   -125.00 -31.00   1.00    5.00    --  -35.00 -15.00-144.00   94
  2  \w   -124.00 -33.00   1.00    5.00    --  -35.00 -72.00-180.00   91
  3  \w    -50.00  40.00   1.00    5.00    --  -35.00  72.00-144.00   90
  4  \w    -50.00  40.00   1.00    5.00    --  -35.00  43.00-180.00   90
  5  \w   -125.00 -32.00   1.00   20.00    -- -110.00  72.00-180.00   93
  6  \w   -125.00 -25.00   1.00   20.00    -- -110.00  14.00-180.00  100
  7  \w   -115.00 -25.00   1.00   20.00    -- -110.00  72.00-108.00   90
  8  \w   -115.00 -25.00   1.00   20.00    -- -110.00  14.00 -36.00   90
  9  \w   -200.00-110.00   1.00   20.00    -- -110.00 -72.00-180.00   90
 10  \w   -200.00-110.00   1.00   20.00    -- -110.00 -15.00-108.00   90
 11  \w   -124.00 -32.00   1.00   20.00    -- -110.00  72.00-144.00   92
 12  \w   -195.00-105.00   1.00   20.00    -- -110.00 -44.00-144.00   90
 13  \w   -111.00 -20.00   1.00   20.00    -- -110.00  72.00 -72.00   91
 14  \w   -200.00-110.00   1.00   20.00    -- -110.00 -72.00-144.00   90
;
_diffrn_measurement_device       'AFC12 (Right): Kappa 3 circle'
_diffrn_measurement_device_type  'Rigaku Pilatus 200K'
_diffrn_measurement_method       '\w scans'
_diffrn_measurement_specimen_support Fiber
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0493243000
_diffrn_orient_matrix_UB_12      0.0655928000
_diffrn_orient_matrix_UB_13      -0.0636361000
_diffrn_orient_matrix_UB_21      0.0448423000
_diffrn_orient_matrix_UB_22      -0.0886387000
_diffrn_orient_matrix_UB_23      -0.0462701000
_diffrn_orient_matrix_UB_31      -0.2297736000
_diffrn_orient_matrix_UB_32      -0.0033387000
_diffrn_orient_matrix_UB_33      -0.0226631000
_diffrn_radiation_monochromator  confocal
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0205
_diffrn_reflns_av_unetI/netI     0.0106
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            13103
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.976
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         78.838
_diffrn_reflns_theta_min         3.941
_diffrn_source                   'rotating anode'
_diffrn_source_current           30.0
_diffrn_source_power             1.2
_diffrn_source_type              'Rigaku MM007-HF Cu'
_diffrn_source_voltage           40.0
_exptl_absorpt_coefficient_mu    0.623
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.84635
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.41 (Rigaku Oxford Diffraction, 2015)
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    1.187
_exptl_crystal_description       plate
_exptl_crystal_F_000             656
_exptl_crystal_preparation       Fiber
_exptl_crystal_size_max          0.32
_exptl_crystal_size_mid          0.26
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.199
_refine_diff_density_min         -0.216
_refine_diff_density_rms         0.055
_refine_ls_abs_structure_details
;
 Flack x determined using 1461 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.02(4)
_refine_ls_extinction_coef       0.0129(9)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2014/7 (Sheldrick 2014'
_refine_ls_goodness_of_fit_ref   1.041
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     206
_refine_ls_number_reflns         3566
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.041
_refine_ls_R_factor_all          0.0322
_refine_ls_R_factor_gt           0.0321
_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^)+(0.0510P)^2^+0.3220P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0848
_refine_ls_wR_factor_ref         0.0850
_reflns_Friedel_coverage         0.711
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.964
_reflns_number_gt                3536
_reflns_number_total             3566
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ol6b00369_si_002.cif
_cod_data_source_block           p20151222a
_cod_database_code               1555500
_chemical_oxdiff_formula         C19H26O3
_shelx_estimated_absorpt_t_max   0.929
_shelx_estimated_absorpt_t_min   0.825
_reflns_odcompleteness_completeness 98.46
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     78.60
_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:
 C2(H2), C7(H7)
2.b Secondary CH2 refined with riding coordinates:
 C4(H4A,H4B), C5(H5A,H5B)
2.c Aromatic/amide H refined with riding coordinates:
 C13(H13), C15(H15)
2.d Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C16(H16A,H16B,H16C), C17(H17A,H17B,H17C),
 C18(H18A,H18B,H18C), C19(H19A,H19B,H19C)
;
_shelx_res_checksum              36331
_shelx_hkl_checksum              42098
_shelx_shelxl_version_number     2014/7
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.481
_oxdiff_exptl_absorpt_empirical_full_min 0.653