Total synthesis of atropodiastereomers of heterodimeric <i>Amaryllidaceae</i> alkaloids: narcipavline and narcikachnine.
Pal, Souvik; Majumder, Satyajit; Niyogi, Sovan; Shyamal, Pranay; Mondal, Debabrata; Das, Bishnu; Bisai, Alakesh; Chemical science 15 (2024) 19851–19857; doi:10.1039/d4sc04361h

data_1573065
_publ_section_title
;
 Total synthesis of atropodiastereomers of heterodimeric
 <i>Amaryllidaceae</i> alkaloids: narcipavline and narcikachnine.
;
_journal_issue                   47
_journal_name_full               'Chemical science'
_journal_page_first              19851
_journal_page_last               19857
_journal_paper_doi               10.1039/d4sc04361h
_journal_volume                  15
_journal_year                    2024
_chemical_absolute_configuration 9S
_chemical_formula_moiety         'C18 H21 I O5'
_chemical_formula_sum            'C18 H21 I O5'
_chemical_formula_weight         444.25
_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   geom
_atom_sites_solution_primary     dual
_audit_block_doi                 10.5517/ccdc.csd.cc2l1910
_audit_creation_date             2024-09-16
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-09-16 deposited with the CCDC.	2024-10-31 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 102.504(3)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   13.1948(3)
_cell_length_b                   4.76050(10)
_cell_length_c                   14.5444(4)
_cell_measurement_reflns_used    6712
_cell_measurement_temperature    99.98(11)
_cell_measurement_theta_max      67.9500
_cell_measurement_theta_min      3.1070
_cell_volume                     891.92(4)
_computing_cell_refinement       'CrysAlisPro 1.171.41.115a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.115a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.115a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.98(11)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix3000
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w    -35.00  24.00   0.50    0.20    --   40.46 -12.00-180.00  118
  2  \w     29.00  83.00   0.50    0.34    --   96.35 -68.00-180.00  108
  3  \w     29.00  83.00   0.50    0.34    --   96.35 -68.00 -60.00  108
  4  \w     28.00  68.00   0.50    0.34    --   96.35 -59.00-120.00   80
  5  \w     30.00  57.00   0.50    0.34    --   96.35 -50.00 -60.00   54
  6  \w     30.00  57.00   0.50    0.34    --   96.35 -50.00-180.00   54
  7  \w    -35.00  24.00   0.50    0.20    --   40.46 -12.00 -47.00  118
  8  \w     30.00  57.00   0.50    0.34    --   96.35 -50.00 -30.00   54
  9  \w     30.00  57.00   0.50    0.34    --   96.35 -50.00   0.00   54
 10  \w     30.00  57.00   0.50    0.34    --   96.35 -50.00  60.00   54
 11  \w     30.00  57.00   0.50    0.34    --   96.35 -50.00  90.00   54
 12  \w     28.00  68.00   0.50    0.34    --   96.35 -59.00 120.00   80
 13  \w     81.00 165.00   0.50    0.34    --   96.35 145.00  60.00  168
 14  \w     30.00  57.00   0.50    0.34    --   96.35 -50.00-150.00   54
 15  \w     23.00 106.00   0.50    0.34    --   96.35 -96.00-120.00  166
 16  \w     18.00  78.00   0.50    0.20    --   40.46-104.00  60.00  120
 17  \w     44.00 127.00   0.50    0.34    --   96.35-145.00  60.00  166
 18  \w     23.00 106.00   0.50    0.34    --   96.35 -96.00  90.00  166
 19  \w     60.00 172.00   0.50    0.34    --   96.35  12.00 124.00  224
 20  \w     81.00 167.00   0.50    0.34    --   96.35  25.00  30.00  172
 21  \w     75.00 165.00   0.50    0.34    --   96.35  59.00 150.00  180
 22  \w     71.00 170.00   0.50    0.34    --   96.35  17.00 -30.00  198
 23  \w     81.00 167.00   0.50    0.34    --   96.35  25.00-150.00  172
 24  \w     75.00 165.00   0.50    0.34    --   96.35  59.00-120.00  180
 25  \w     70.00 165.00   0.50    0.34    --   96.35  77.00 -60.00  190
 26  \w     14.00 109.00   0.50    0.20    --   40.46  77.00 120.00  190
 27  \w      4.00 116.00   0.50    0.20    --   40.46  12.00 124.00  224
 28  \w     14.00 109.00   0.50    0.20    --   40.46  77.00  90.00  190
 29  \w     14.00 109.00   0.50    0.20    --   40.46  77.00  30.00  190
 30  \w     17.00 108.00   0.50    0.20    --   40.46  64.00-150.00  182
 31  \w    -64.00  27.00   0.50    0.20    --  -40.46  64.00  60.00  182
 32  \w    -24.00  35.00   0.50    0.20    --  -40.46  12.00 124.00  118
 33  \w    -57.00  26.00   0.50    0.20    --  -40.46  50.00 -30.00  166
 34  \w    -24.00  35.00   0.50    0.20    --  -40.46  12.00 -60.00  118
 35  \w    -57.00  26.00   0.50    0.20    --  -40.46  50.00-120.00  166
 36  \w   -158.00 -48.00   0.50    0.34    --  -82.50 -12.00 -47.00  220
 37  \w   -109.00 -13.00   0.50    0.20    --  -40.46 -77.00 -30.00  192
 38  \w   -109.00 -13.00   0.50    0.20    --  -40.46 -77.00-120.00  192
 39  \w   -108.00 -17.00   0.50    0.20    --  -40.46 -64.00 -90.00  182
 40  \w   -107.00 -21.00   0.50    0.20    --  -40.46 -50.00-180.00  172
 41  \w    -47.00 -15.00   0.50    0.34    --  -82.50  42.00-120.00   64
 42  \w   -116.00  -6.00   0.50    0.20    --  -40.46 -12.00 -47.00  220
 43  \w    -80.00  -9.00   0.50    0.34    --  -82.50  96.00 120.00  142
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix3000'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1029573000
_diffrn_orient_matrix_UB_12      -0.0404362000
_diffrn_orient_matrix_UB_13      0.0724297000
_diffrn_orient_matrix_UB_21      0.0578775000
_diffrn_orient_matrix_UB_22      -0.0314266000
_diffrn_orient_matrix_UB_23      -0.0807797000
_diffrn_orient_matrix_UB_31      0.0186705000
_diffrn_orient_matrix_UB_32      0.3195334000
_diffrn_orient_matrix_UB_33      0.0013240000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0499
_diffrn_reflns_av_unetI/netI     0.0439
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       5
_diffrn_reflns_limit_k_min       -4
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            9822
_diffrn_reflns_point_group_measured_fraction_full 0.839
_diffrn_reflns_point_group_measured_fraction_max 0.837
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.022
_diffrn_reflns_theta_min         3.112
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    14.318
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.18896
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.115a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.654
_exptl_crystal_description       needle
_exptl_crystal_F_000             444
_exptl_crystal_size_max          0.54
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.935
_refine_diff_density_min         -1.055
_refine_diff_density_rms         0.099
_refine_ls_abs_structure_details
;
 Flack x determined using 811 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.028(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.079
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     219
_refine_ls_number_reflns         2723
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.079
_refine_ls_R_factor_all          0.0323
_refine_ls_R_factor_gt           0.0309
_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^)+(0.0444P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0764
_refine_ls_wR_factor_ref         0.0774
_reflns_Friedel_coverage         0.487
_reflns_Friedel_fraction_full    0.633
_reflns_Friedel_fraction_max     0.630
_reflns_number_gt                2575
_reflns_number_total             2723
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc04361h2.cif
_cod_data_source_block           ab_aya_sp02336r_souvik
_cod_depositor_comments
'Adding full bibliography for 1573064--1573066.cif.'
_cod_database_code               1573065
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H O I'
_chemical_oxdiff_usercomment     '100 K'
_shelx_estimated_absorpt_t_max   0.598
_shelx_estimated_absorpt_t_min   0.048
_olex2_refinement_description
;
1.a Ternary CH refined with riding coordinates:
 C9(H9)
1.b Secondary CH2 refined with riding coordinates:
 C15(H15A,H15B), C13(H13A,H13B), C14(H14A,H14B), C12(H12A,H12B), C17(H17A,H17B)
1.c Aromatic/amide H refined with riding coordinates:
 C11(H11), C4(H4), C8(H8), C3(H3)
1.d Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C18(H18A,H18B,H18C)
;
_shelx_res_checksum              22256
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 3.693
_oxdiff_exptl_absorpt_empirical_full_min 0.518