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_4128795
_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         'C38 H43 N3 O8, C H4 O'
_chemical_formula_sum            'C39 H47 N3 O9'
_chemical_formula_weight         701.79
_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'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_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                 96.4570(10)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   10.65440(10)
_cell_length_b                   15.3909(2)
_cell_length_c                   10.78350(10)
_cell_measurement_reflns_used    9071
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      70.79
_cell_measurement_theta_min      4.13
_cell_volume                     1757.07(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 1.000
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device       'Fixed Chi Three-Circle Diffractometer'
_diffrn_measurement_device_type  'Bruker D8 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  0.0242
_diffrn_reflns_av_unetI/netI     0.0104
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            58779
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.989
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         71.154
_diffrn_reflns_theta_min         4.126
_diffrn_source                   'Micro Focus Rotating Anode'
_diffrn_source_type              'Rigaku MicroMax-007HF'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.773
_exptl_absorpt_correction_T_max  0.7534
_exptl_absorpt_correction_T_min  0.6788
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.0487 before and 0.0331 after correction. The Ratio of minimum to maximum transmission is 0.9010. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            'light yellow'
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.326
_exptl_crystal_description       block
_exptl_crystal_F_000             748
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.17
_exptl_crystal_size_min          0.125
_refine_diff_density_max         0.202
_refine_diff_density_min         -0.140
_refine_diff_density_rms         0.028
_refine_ls_abs_structure_details
;
 Flack x determined using 3169 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.014(19)
_refine_ls_extinction_coef       0.0018(2)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2016/6 (Sheldrick 2016)'
_refine_ls_goodness_of_fit_ref   1.029
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     527
_refine_ls_number_reflns         6707
_refine_ls_number_restraints     5
_refine_ls_restrained_S_all      1.030
_refine_ls_R_factor_all          0.0243
_refine_ls_R_factor_gt           0.0243
_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^)+(0.0383P)^2^+0.3252P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0642
_refine_ls_wR_factor_ref         0.0643
_reflns_Friedel_coverage         0.908
_reflns_Friedel_fraction_full    0.995
_reflns_Friedel_fraction_max     0.980
_reflns_number_gt                6688
_reflns_number_total             6707
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b06968_si_002.cif
_cod_data_source_block           boger100
_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               4128795
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.910
_shelx_estimated_absorpt_t_min   0.873
_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. Restrained distances
 C9-C12 \\sim C9A-C12A
 with sigma of 0.01
 C9A-C10A \\sim C9-C10
 with sigma of 0.01
 C11A-C10A \\sim C11-C10
 with sigma of 0.01
 O7-C12 \\sim O8A-C12A
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
Uanis(C9A) = Uanis(C9)
Uanis(C11) = Uanis(C11A)
4. Others
 Sof(O7A)=Sof(O8A)=Sof(C9A)=Sof(C10A)=Sof(H10C)=Sof(H10D)=Sof(C11A)=Sof(H11C)=
 Sof(H11D)=Sof(C12A)=Sof(C13A)=Sof(H13D)=Sof(H13E)=Sof(H13F)=1-FVAR(1)
 Sof(O7)=Sof(O8)=Sof(C9)=Sof(C10)=Sof(H10A)=Sof(H10B)=Sof(C11)=Sof(H11A)=
 Sof(H11B)=Sof(C12)=Sof(C13)=Sof(H13A)=Sof(H13B)=Sof(H13C)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C22(H22), C26(H26), C37(H37)
5.b Secondary CH2 refined with riding coordinates:
 C10(H10A,H10B), C10A(H10C,H10D), C11(H11A,H11B), C11A(H11C,H11D), C32(H32A,
 H32B), C36(H36A,H36B), C38(H38A,H38B), C39(H39A,H39B)
5.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3B), C4(H4), C5(H5), C17(H17), C20(H20), C34(H34), C35(H35)
5.d Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C13A(H13D,H13E,H13F), C16(H16A,H16B,H16C), C21(H21A,H21B,
 H21C), C29(H29A,H29B,H29C), C31(H31A,H31B,H31C), C33(H33A,H33B,H33C), C40(H40A,
 H40B,H40C)
5.e Idealised tetrahedral OH refined as rotating group:
 O9(H9)
5.f Idealised tetrahedral OH refined as rotating group with stretchable bonds:
 O3(H3)
;
_shelx_res_checksum              22851
_shelx_hkl_checksum              83890
_olex2_submission_special_instructions 'No special instructions were received'