Enantioselective Total Synthesis of (–)-Colchicine, (+)-Demecolcinone and Metacolchicine: Determination of the Absolute Configurations of the Latter Two Alkaloids
Chen, Bo; Liu, Xin; Hu, Ya-Jian; Zhang, Dongmei; Deng, Lijuan; Lu, Jieyu; Min, Long; Ye, Wen-Cai; Li, Chuang-Chuang; Chem. Sci.  (2017) –; doi:10.1039/C7SC01341H

data_1545997
_publ_section_title
;
 Enantioselective Total Synthesis of (--)-Colchicine, (+)-Demecolcinone
 and Metacolchicine: Determination of the Absolute Configurations of the
 Latter Two Alkaloids
;
_journal_name_full               'Chem. Sci.'
_journal_paper_doi               10.1039/C7SC01341H
_journal_year                    2017
_chemical_absolute_configuration unk
_chemical_formula_moiety         'C21 H23 N O6'
_chemical_formula_sum            'C21 H23 N O6'
_chemical_formula_weight         385.40
_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'
_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
_audit_creation_date             2016-12-23
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r1)
;
_audit_update_record
;
2017-05-03 deposited with the CCDC.
2017-05-05 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.760(3)
_cell_length_b                   13.957(5)
_cell_length_c                   16.322(5)
_cell_measurement_reflns_used    2141
_cell_measurement_temperature    293
_cell_measurement_theta_max      67.8
_cell_measurement_theta_min      23.0
_cell_volume                     1995.6(12)
_computing_cell_refinement
;
CrystalClear-SM Expert 2.0 r4 (Rigaku, 2009)
;
_computing_data_collection
;
CrystalClear-SM Expert 2.0 r4 (Rigaku, 2009)
;
_computing_data_reduction
;
CrystalClear-SM Expert 2.0 r4 (Rigaku, 2009)
;
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      293
_diffrn_detector                 CCD
_diffrn_detector_area_resol_mean 22.2222
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_details
;
scan:
    Number of images: 180
               Slice: -134.0000 - 46.0000
         Image width: 1.0000
            Exp time: 15.0000
       Rotation axis: Omega
               Omega: 0.0000
                 Chi: 54.0000
                 Phi: 90.0000
                 XTD: 45.2664
              2theta: -44.0654
scan:
    Number of images: 177
               Slice: -134.0000 - 43.0000
         Image width: 1.0000
            Exp time: 15.0000
       Rotation axis: Omega
               Omega: 0.0000
                 Chi: 54.0000
                 Phi: 270.0000
                 XTD: 45.2664
              2theta: -44.0654
scan:
    Number of images: 120
               Slice: -104.0000 - 16.0000
         Image width: 1.0000
            Exp time: 15.0000
       Rotation axis: Omega
               Omega: 0.0000
                 Chi: 30.0000
                 Phi: 0.0000
                 XTD: 45.2664
              2theta: -44.0654
scan:
    Number of images: 45
               Slice: -111.0000 - -66.0000
         Image width: 1.0000
            Exp time: 15.0000
       Rotation axis: Omega
               Omega: 0.0000
                 Chi: 45.0000
                 Phi: 180.0000
                 XTD: 45.2664
              2theta: -44.0654
scan:
    Number of images: 180
               Slice: -180.0000 - 0.0000
         Image width: 1.0000
            Exp time: 15.0000
       Rotation axis: Omega
               Omega: 0.0000
                 Chi: 54.0000
                 Phi: 120.0000
                 XTD: 45.2664
              2theta: -90.0654
scan:
    Number of images: 180
               Slice: -180.0000 - 0.0000
         Image width: 1.0000
            Exp time: 15.0000
       Rotation axis: Omega
               Omega: 0.0000
                 Chi: 54.0000
                 Phi: 90.0000
                 XTD: 45.2664
              2theta: -90.0654
scan:
    Number of images: 180
               Slice: -180.0000 - 0.0000
         Image width: 1.0000
            Exp time: 15.0000
       Rotation axis: Omega
               Omega: 0.0000
                 Chi: 54.0000
                 Phi: 0.0000
                 XTD: 45.2664
              2theta: -90.0654
scan:
    Number of images: 180
               Slice: -180.0000 - 0.0000
         Image width: 1.0000
            Exp time: 15.0000
       Rotation axis: Omega
               Omega: 0.0000
                 Chi: 54.0000
                 Phi: 270.0000
                 XTD: 45.2664
              2theta: -90.0654
scan:
    Number of images: 180
               Slice: -180.0000 - 0.0000
         Image width: 1.0000
            Exp time: 15.0000
       Rotation axis: Omega
               Omega: 0.0000
                 Chi: 0.0000
                 Phi: 180.0000
                 XTD: 45.2664
              2theta: -90.0654
scan:
    Number of images: 162
               Slice: -180.0000 - -18.0000
         Image width: 1.0000
            Exp time: 15.0000
       Rotation axis: Omega
               Omega: 0.0000
                 Chi: 54.0000
                 Phi: 240.0000
                 XTD: 45.2664
              2theta: -90.0654
scan:
    Number of images: 156
               Slice: -180.0000 - -24.0000
         Image width: 1.0000
            Exp time: 15.0000
       Rotation axis: Omega
               Omega: 0.0000
                 Chi: 54.0000
                 Phi: 180.0000
                 XTD: 45.2664
              2theta: -90.0654
scan:
    Number of images: 150
               Slice: -180.0000 - -30.0000
         Image width: 1.0000
            Exp time: 15.0000
       Rotation axis: Omega
               Omega: 0.0000
                 Chi: 45.0000
                 Phi: 240.0000
                 XTD: 45.2664
              2theta: -90.0654
scan:
    Number of images: 135
               Slice: -180.0000 - -45.0000
         Image width: 1.0000
            Exp time: 15.0000
       Rotation axis: Omega
               Omega: 0.0000
                 Chi: 45.0000
                 Phi: 90.0000
                 XTD: 45.2664
              2theta: -90.0654
scan:
    Number of images: 110
               Slice: -180.0000 - -70.0000
         Image width: 1.0000
            Exp time: 15.0000
       Rotation axis: Omega
               Omega: 0.0000
                 Chi: 45.0000
                 Phi: 0.0000
                 XTD: 45.2664
              2theta: -90.0654
;
_diffrn_measurement_device
;
AFC11 (Right): Eulerian 3 circle
;
_diffrn_measurement_device_type  'Rigaku Saturn944+ (2x2 bin mode)'
_diffrn_measurement_method       'profile data from \w-scans'
_diffrn_measurement_specimen_support Fiber
_diffrn_orient_matrix_type       d*Trek
_diffrn_orient_matrix_UB_11      0.045782
_diffrn_orient_matrix_UB_12      -0.036628
_diffrn_orient_matrix_UB_13      -0.041182
_diffrn_orient_matrix_UB_21      -0.062348
_diffrn_orient_matrix_UB_22      -0.094483
_diffrn_orient_matrix_UB_23      0.014723
_diffrn_orient_matrix_UB_31      -0.033181
_diffrn_orient_matrix_UB_32      0.014181
_diffrn_orient_matrix_UB_33      -0.049511
_diffrn_radiation_monochromator  'Graphite Monochromator'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1949
_diffrn_reflns_av_unetI/netI     0.0759
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            31068
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.337
_diffrn_reflns_theta_min         1.920
_diffrn_source                   'Sealed Tube'
_diffrn_source_current           0.9
_diffrn_source_power             0.0
_diffrn_source_voltage           45.0
_exptl_absorpt_coefficient_mu    0.094
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.665
_exptl_absorpt_correction_type   multi-scan
_exptl_crystal_colour            Colorless
_exptl_crystal_density_diffrn    1.283
_exptl_crystal_density_method    "'not measured'"
_exptl_crystal_description       Prism
_exptl_crystal_F_000             816
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.407
_refine_diff_density_min         -0.204
_refine_diff_density_rms         0.055
_refine_ls_abs_structure_details
;
 Flack x determined using 895 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   2.3(10)
_refine_ls_extinction_coef       0.35(4)
_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   1.087
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     258
_refine_ls_number_reflns         3622
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.089
_refine_ls_R_factor_all          0.0889
_refine_ls_R_factor_gt           0.0795
_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^)+(0.1857P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2400
_refine_ls_wR_factor_ref         0.2659
_reflns_Friedel_coverage         0.741
_reflns_Friedel_fraction_full    0.997
_reflns_Friedel_fraction_max     0.991
_reflns_number_gt                2834
_reflns_number_total             3622
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7sc01341h2.cif
_cod_data_source_block           a
_cod_depositor_comments
;
The following automatic conversions were performed:

'_exptl_absorpt_correction_type' value 'Multi-scan' changed to
'multi-scan' according to
/home/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 4973 2017-02-22 13:04:09Z antanas 
;
_cod_original_cell_volume        1995.7(11)
_cod_database_code               1545997
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Rigid bond restraints
 C28, O14
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
3.a Ternary CH refined with riding coordinates:
 C19(H19), C25(H25)
3.b Secondary CH2 refined with riding coordinates:
 C18(H18A,H18B), C21(H21A,H21B)
3.c Aromatic/amide H refined with riding coordinates:
 N4(H4), C12(H12), C13(H13), C22(H22), C23(H23)
3.d Idealised Me refined as rotating group:
 C20(H20A,H20B,H20C), C24(H24A,H24B,H24C), C26(H26A,H26B,H26C), C27(H27A,H27B,
 H27C)
;
_shelx_res_checksum              59737
_shelx_hkl_checksum              66612
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'