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_1545998
_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         'C36 H31 N3 O12, C4 H5 O2'
_chemical_formula_sum            'C40 H36 N3 O14'
_chemical_formula_weight         782.72
_chemical_name_systematic        liux-1
_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'
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_audit_block_doi                 10.5517/ccdc.csd.cc1n56z0
_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
;
2016-12-24 deposited with the CCDC.
2017-05-05 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 105.103(18)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   13.869(9)
_cell_length_b                   9.736(8)
_cell_length_c                   14.969(11)
_cell_measurement_reflns_used    1874
_cell_measurement_temperature    293
_cell_measurement_theta_max      68.2
_cell_measurement_theta_min      23.3
_cell_volume                     1951(3)
_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)'
_diffrn_ambient_temperature      293
_diffrn_detector                 CCD
_diffrn_detector_area_resol_mean 22.2222
_diffrn_measured_fraction_theta_full 0.982
_diffrn_measured_fraction_theta_max 0.978
_diffrn_measurement_details
;
scan:
    Number of images: 180
               Slice: -134.0000 - 46.0000
         Image width: 1.0000
            Exp time: 6.0000
       Rotation axis: Omega
               Omega: 0.0000
                 Chi: 30.0000
                 Phi: 0.0000
                 XTD: 44.8868
              2theta: -44.3414
scan:
    Number of images: 180
               Slice: -134.0000 - 46.0000
         Image width: 1.0000
            Exp time: 6.0000
       Rotation axis: Omega
               Omega: 0.0000
                 Chi: 45.0000
                 Phi: 240.0000
                 XTD: 44.8868
              2theta: -44.3414
scan:
    Number of images: 150
               Slice: -180.0000 - -30.0000
         Image width: 1.0000
            Exp time: 6.0000
       Rotation axis: Omega
               Omega: 0.0000
                 Chi: 30.0000
                 Phi: 0.0000
                 XTD: 44.8868
              2theta: -90.3414
scan:
    Number of images: 150
               Slice: -180.0000 - -30.0000
         Image width: 1.0000
            Exp time: 6.0000
       Rotation axis: Omega
               Omega: 0.0000
                 Chi: 45.0000
                 Phi: 240.0000
                 XTD: 44.8868
              2theta: -90.3414
scan:
    Number of images: 132
               Slice: -180.0000 - -48.0000
         Image width: 1.0000
            Exp time: 6.0000
       Rotation axis: Omega
               Omega: 0.0000
                 Chi: 54.0000
                 Phi: 120.0000
                 XTD: 44.8868
              2theta: -90.3414
scan:
    Number of images: 129
               Slice: -147.0000 - -18.0000
         Image width: 1.0000
            Exp time: 6.0000
       Rotation axis: Omega
               Omega: 0.0000
                 Chi: 54.0000
                 Phi: 270.0000
                 XTD: 44.8868
              2theta: -90.3414
;
_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      -0.004748
_diffrn_orient_matrix_UB_12      -0.041846
_diffrn_orient_matrix_UB_13      -0.061679
_diffrn_orient_matrix_UB_21      -0.059132
_diffrn_orient_matrix_UB_22      -0.067315
_diffrn_orient_matrix_UB_23      0.050222
_diffrn_orient_matrix_UB_31      -0.055605
_diffrn_orient_matrix_UB_32      0.023737
_diffrn_orient_matrix_UB_33      -0.033655
_diffrn_radiation_monochromator  'Graphite Monochromator'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0860
_diffrn_reflns_av_unetI/netI     0.0867
_diffrn_reflns_Laue_measured_fraction_full 0.982
_diffrn_reflns_Laue_measured_fraction_max 0.978
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            12514
_diffrn_reflns_point_group_measured_fraction_full 0.857
_diffrn_reflns_point_group_measured_fraction_max 0.851
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.361
_diffrn_reflns_theta_min         1.409
_diffrn_source                   'Sealed Tube'
_diffrn_source_current           0.9
_diffrn_source_power             0.0
_diffrn_source_voltage           45.0
_exptl_absorpt_coefficient_mu    0.102
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.593
_exptl_absorpt_correction_type   multi-scan
_exptl_crystal_colour            Colorless
_exptl_crystal_density_diffrn    1.332
_exptl_crystal_density_method    "'not measured'"
_exptl_crystal_description       Prism
_exptl_crystal_F_000             818
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.410
_refine_diff_density_min         -0.254
_refine_diff_density_rms         0.071
_refine_ls_abs_structure_details
;
 Flack x determined using 1025 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.5(10)
_refine_ls_extinction_coef       0.38(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   1.023
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     515
_refine_ls_number_reflns         6095
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.023
_refine_ls_R_factor_all          0.1221
_refine_ls_R_factor_gt           0.0992
_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          0.2557
_refine_ls_wR_factor_ref         0.3148
_reflns_Friedel_coverage         0.637
_reflns_Friedel_fraction_full    0.714
_reflns_Friedel_fraction_max     0.707
_reflns_number_gt                3344
_reflns_number_total             6095
_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_database_code               1545998
_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:
 C7(H7)
2.b Secondary CH2 refined with riding coordinates:
 C14(H14A,H14B), C32(H32A,H32B), C41(H41A,H41B), C51(H51A,H51B)
2.c Me refined with riding coordinates:
 C44(H44A,H44B,H44C), C45(H45A,H45B,H45C), C47(H47A,H47B,H47C), C48(H48A,H48B,
 H48C), C52(H52A,H52B,H52C)
2.d Aromatic/amide H refined with riding coordinates:
 C9(H9), C17(H17), C19(H19), C22(H22), C23(H23), C26(H26), C30(H30), C36(H36),
 C37(H37), C40(H40), C43(H43), C46(H46)
;
_shelx_res_checksum              95677
_shelx_hkl_checksum              2378
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'