Divergent enantioselective synthesis of hapalindole-type alkaloids using catalytic asymmetric hydrogenation of a ketone to construct the chiral core structure
Liu, Yang; Cheng, Li-Jie; Yue, Hai-Tao; Che, Wen; Xie, Jian-Hua; Zhou, Qi-Lin; Chem. Sci. 7 (2016) 4725–; doi:10.1039/C6SC00686H

data_1543106
_publ_section_title
;
 Divergent enantioselective synthesis of hapalindole-type alkaloids using
 catalytic asymmetric hydrogenation of a ketone to construct the chiral
 core structure
;
_journal_issue                   7
_journal_name_full               'Chem. Sci.'
_journal_page_first              4725
_journal_paper_doi               10.1039/C6SC00686H
_journal_volume                  7
_journal_year                    2016
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C23 H27 N O4 S, C3 H6 O'
_chemical_formula_sum            'C26 H33 N O5 S'
_chemical_formula_weight         471.59
_chemical_name_systematic        7
_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'
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2016-01-15
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_audit_update_record
;
2016-02-15 deposited with the CCDC.
2016-04-12 downloaded from the CCDC.
;
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   7.8163(16)
_cell_length_b                   11.555(2)
_cell_length_c                   26.919(5)
_cell_measurement_reflns_used    4760
_cell_measurement_temperature    133.1500
_cell_measurement_theta_max      25.0091
_cell_measurement_theta_min      1.5130
_cell_volume                     2431.3(8)
_computing_cell_refinement       'CrystalClear (Rigaku Inc., 2008)'
_computing_data_collection       'CrystalClear (Rigaku Inc., 2008)'
_computing_data_reduction        'CrystalClear (Rigaku Inc., 2008)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution
;
????
;
_diffrn_ambient_temperature      133.1500
_diffrn_detector_area_resol_mean 28.5714
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_details
;
scan:
    Number of images: 180
               Slice: -110.0000 - 70.0000
         Image width: 1.0000
            Exp time: 30.0000
       Rotation axis: Omega
               Omega: 0.0000
                 Chi: 45.0000
                 Phi: 0.0000
                 XTD: 45.1138
              2theta: -19.9427
scan:
    Number of images: 150
               Slice: -110.0000 - 40.0000
         Image width: 1.0000
            Exp time: 30.0000
       Rotation axis: Omega
               Omega: 0.0000
                 Chi: 45.0000
                 Phi: 90.0000
                 XTD: 45.1138
              2theta: -19.9427
scan:
    Number of images: 100
               Slice: -110.0000 - -10.0000
         Image width: 1.0000
            Exp time: 30.0000
       Rotation axis: Omega
               Omega: 0.0000
                 Chi: 45.0000
                 Phi: 180.0000
                 XTD: 45.1138
              2theta: -19.9427
;
_diffrn_measurement_device
;
Saturn70 (4x4 bin mode)
;
_diffrn_measurement_device_details
;
AFC10: Fixed Chi 2 circle
;
_diffrn_measurement_device_type  'Bruker P4'
_diffrn_measurement_method       dtprofit.ref
_diffrn_orient_matrix_type       d*Trek
_diffrn_orient_matrix_UB_11      0.1249
_diffrn_orient_matrix_UB_12      -0.0108
_diffrn_orient_matrix_UB_13      -0.0256
_diffrn_orient_matrix_UB_21      0.0100
_diffrn_orient_matrix_UB_22      -0.0502
_diffrn_orient_matrix_UB_23      0.0698
_diffrn_orient_matrix_UB_31      -0.0068
_diffrn_orient_matrix_UB_32      -0.0301
_diffrn_orient_matrix_UB_33      -0.0207
_diffrn_radiation_detector       CCD
_diffrn_radiation_monochromator  Confocal
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1047
_diffrn_reflns_av_unetI/netI     0.0995
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            19854
_diffrn_reflns_theta_full        24.99
_diffrn_reflns_theta_max         24.99
_diffrn_reflns_theta_min         1.51
_diffrn_source                   'Rotating Anode'
_diffrn_source_current           40.0000
_diffrn_source_power             2.0000
_diffrn_source_voltage           50.0000
_exptl_absorpt_coefficient_mu    0.170
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.6282
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   crystalclear
_exptl_crystal_colour            Colorless
_exptl_crystal_density_diffrn    1.288
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       Prism
_exptl_crystal_F_000             1008
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: diethyl ether/hexane'
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.301
_refine_diff_density_min         -0.476
_refine_diff_density_rms         0.085
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.09(18)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.128
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     304
_refine_ls_number_reflns         4263
_refine_ls_number_restraints     24
_refine_ls_restrained_S_all      1.126
_refine_ls_R_factor_all          0.1148
_refine_ls_R_factor_gt           0.0837
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0899P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1899
_refine_ls_wR_factor_ref         0.2057
_reflns_number_gt                3143
_reflns_number_total             4263
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            c6sc00686h2.cif
_cod_data_source_block           shelxl
_cod_depositor_comments
;
The following automatic conversions were performed:

'_exptl_absorpt_correction_type' value 'Multi-scan' changed to
'multi-scan' according to
/usr/data/users/saulius/crontab/automatic-downloads/rss-feeds/RSC/lib/dictionaries/cif_core.dic
dictionary named 'cif_core.dic' version 2.4.2 from 2011-04-26.

Automatic conversion script
Id: cif_fix_values 4268 2015-11-12 08:31:59Z antanas 

 Adding full bibliography for 1543106.cif.
;
_cod_original_cell_volume        2431.2(8)
_cod_database_code               1543106
_diffrn_number_total             2482
_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, All O(H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(O5) \\sim Ueq, Uanis(C24) \\sim Ueq, Uanis(C25) \\sim Ueq, Uanis(C26)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
3.a Ternary CH refined with riding coordinates:
 C15(H15), C16(H16), C20(H20)
3.b Secondary CH2 refined with riding coordinates:
 C17(H17A,H17B), C18(H18A,H18B), C19(H19A,H19B)
3.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3A), C4(H4A), C5(H5), C6(H6), C8(H8), C9(H9), C10(H10), C11(H11),
 C14(H14)
3.d Idealised Me refined as rotating group:
 C22(H22A,H22B,H22C), C23(H23A,H23B,H23C), C24(H24A,H24B,H24C), C26(H26A,H26B,
 H26C)
3.e Idealised tetrahedral OH refined as rotating group:
 O3(H3), O4(H4)
;
_olex2_submission_special_instructions 'No special instructions were received'