Triarylaminium Radical Cation Promoted Coupling of Catharanthine with Vindoline: Diastereospecific Synthesis of Anhydrovinblastine and Reaction Scope.
Boon, Byron A.; Boger, Dale L.; Journal of the American Chemical Society 141 (2019) 14349–14355; doi:10.1021/jacs.9b06968

data_4128794
_publ_section_title
;
 Triarylaminium Radical Cation Promoted Coupling of Catharanthine with
 Vindoline: Diastereospecific Synthesis of Anhydrovinblastine and Reaction
 Scope.
;
_journal_issue                   36
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              14349
_journal_page_last               14355
_journal_paper_doi               10.1021/jacs.9b06968
_journal_volume                  141
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C39 H45 N3 O8'
_chemical_formula_sum            'C39 H45 N3 O8'
_chemical_formula_weight         683.78
_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
_audit_creation_date             2019-08-12
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   8.1852(2)
_cell_length_b                   30.4869(7)
_cell_length_c                   31.5036(8)
_cell_measurement_reflns_used    7351
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      68.23
_cell_measurement_theta_min      2.81
_cell_volume                     7861.5(3)
_computing_cell_refinement       'SAINT v8.38A (Bruker, 2017)'
_computing_data_collection       'APEX3 v2017.3-0 (Bruker, 2017)'
_computing_data_reduction        'SAINT v8.38A (Bruker, 2017)'
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.0
_diffrn_detector                 'Bruker APEX-II CCD'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD Area Detector'
_diffrn_measured_fraction_theta_full 0.978
_diffrn_measured_fraction_theta_max 0.977
_diffrn_measurement_device       'Kappa Four-Circle Diffractometer'
_diffrn_measurement_device_type  'Bruker X8 APEX II'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'Double Bounce Multilayer Mirrors'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.1007
_diffrn_reflns_av_unetI/netI     0.0854
_diffrn_reflns_Laue_measured_fraction_full 0.978
_diffrn_reflns_Laue_measured_fraction_max 0.977
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -33
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -37
_diffrn_reflns_number            54822
_diffrn_reflns_point_group_measured_fraction_full 0.979
_diffrn_reflns_point_group_measured_fraction_max 0.977
_diffrn_reflns_theta_full        67.500
_diffrn_reflns_theta_max         68.304
_diffrn_reflns_theta_min         2.017
_diffrn_source                   'Micro Focus Rotating Anode'
_diffrn_source_type              'Bruker Microstar FR-592'
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_exptl_absorpt_coefficient_mu    0.660
_exptl_absorpt_correction_T_max  0.7515
_exptl_absorpt_correction_T_min  0.6943
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.0994 before and 0.0657 after correction. The Ratio of minimum to maximum transmission is 0.9239. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.155
_exptl_crystal_description       irregular
_exptl_crystal_F_000             2912
_exptl_crystal_size_max          0.125
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.015
_refine_diff_density_max         0.320
_refine_diff_density_min         -0.208
_refine_diff_density_rms         0.045
_refine_ls_abs_structure_details
;
 Flack x determined using 3488 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.07(13)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.963
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     915
_refine_ls_number_reflns         14071
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      0.963
_refine_ls_R_factor_all          0.0813
_refine_ls_R_factor_gt           0.0506
_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^)+(0.0528P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1043
_refine_ls_wR_factor_ref         0.1161
_reflns_Friedel_coverage         0.798
_reflns_Friedel_fraction_full    0.980
_reflns_Friedel_fraction_max     0.977
_reflns_number_gt                10134
_reflns_number_total             14071
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b06968_si_003.cif
_cod_data_source_block           boger101_sq
_cod_depositor_comments
;
The following automatic conversions were performed:

data item '_diffrn_radiation_probe' value 'X-ray' was changed to
'x-ray' in accordance with the
/home/data/users/saulius/crontab/automatic-downloads/current/ACS/lib/dictionaries/cif_core.dic
dictionary named 'cif_core.dic' version 2.4.2 last updated on
2011-04-26.

Automatic conversion script
Id: cif_fix_values 6909 2019-04-08 15:41:33Z antanas 
;
_cod_database_code               4128794
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.990
_shelx_estimated_absorpt_t_min   0.922
_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, All O(H) groups
2.a Ternary CH refined with riding coordinates:
 C3(H3A), C7(H7), C11(H11), C3'(H3'A), C7'(H7'), C11'(H11')
2.b Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B), C10(H10A,H10B), C13(H13A,H13B), C17(H17A,H17B), C29(H29A,H29B),
 C30(H30A,H30B), C31(H31A,H31B), C9'(H9'A,H9'B), C10'(H10C,H10D), C13'(H13C,
 H13D), C17'(H17C,H17D), C29'(H29C,H29D), C30'(H30C,H30D), C31'(H31C,H31D)
2.c Aromatic/amide H refined with riding coordinates:
 N3(H3), C15(H15), C16(H16), C21(H21), C24(H24), C36(H36), C37(H37), C38(H38),
 C39(H39), N3'(H3'), C15'(H15'), C16'(H16'), C21'(H21'), C24'(H24'), C36'(H36'),
  C37'(H37'), C38'(H38'), C39'(H39')
2.d Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C6(H6A,H6B,H6C), C14(H14A,H14B,H14C), C18(H18A,H18B,H18C),
 C25(H25A,H25B,H25C), C28(H28A,H28B,H28C), C1'(H1'A,H1'B,H1'C), C6'(H6'A,H6'B,
 H6'C), C14'(H14D,H14E,H14F), C18'(H18D,H18E,H18F), C25'(H25D,H25E,H25F),
 C28'(H28D,H28E,H28F)
2.e Idealised tetrahedral OH refined as rotating group:
 O5(H5), O5'(H5')
;
_shelx_res_checksum              61234
_shelx_hkl_checksum              12740
_shelx_fab_checksum              87206
_olex2_submission_special_instructions 'No special instructions were received'