Phthalideisoquinoline Hemiacetal Alkaloids from <i>Corydalis decumbens</i> That Inhibit Spontaneous Calcium Oscillations, Including Alkyl Derivatives of (+)-Egenine That Are Strikingly Levorotatory.
Zhang, Chun-Lei; Huang, Qi-Long; Chen, Juan; Zhang, Wan-Jin; Jin, Hai-Xiao; Wang, Hong-Bo; Naman, C. Benjamin; Cao, Zheng-Yu; Journal of natural products 82 (2019) 2713–2720; doi:10.1021/acs.jnatprod.9b00247

data_1552590
_publ_section_title
;
 Phthalideisoquinoline Hemiacetal Alkaloids from <i>Corydalis
 decumbens</i> That Inhibit Spontaneous Calcium Oscillations, Including
 Alkyl Derivatives of (+)-Egenine That Are Strikingly Levorotatory.
;
_journal_issue                   10
_journal_name_full               'Journal of natural products'
_journal_page_first              2713
_journal_page_last               2720
_journal_paper_doi               10.1021/acs.jnatprod.9b00247
_journal_volume                  82
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C23 H27 N O6, 6(O)'
_chemical_formula_sum            'C23 H27 N O12'
_chemical_formula_weight         509.45
_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_creation_date             2018-09-29
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 101.1180(13)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   16.2110(2)
_cell_length_b                   8.33626(11)
_cell_length_c                   19.9088(3)
_cell_measurement_reflns_used    14577
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      73.4250
_cell_measurement_theta_min      2.7480
_cell_volume                     2639.96(6)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2684
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.978
_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    -55.00  29.00   1.00    1.00    --  -41.11  38.00  90.00   84
  2  \w    -66.00  33.00   1.00    1.00    --  -41.11  38.00 -60.00   99
  3  \w      2.00  67.00   1.00    1.00    --   41.11 -99.00   0.00   65
  4  \w     34.00 100.00   1.00    1.20    --  106.95-125.00  60.00   66
  5  \w     79.00 120.00   1.00    1.20    --  106.95-125.00 120.00   41
  6  \w     49.00 124.00   1.00    1.20    --  106.95 -45.00  90.00   75
  7  \w     55.00 130.00   1.00    1.20    --  106.95  15.00 -60.00   75
  8  \w     99.00 177.00   1.00    1.20    --  106.95  45.00 -60.00   78
  9  \w    109.00 173.00   1.00    1.20    --  106.95  61.00-180.00   64
 10  \w    103.00 174.00   1.00    1.20    --  106.95 125.00-120.00   71
 11  \w     82.00 140.00   1.00    1.20    --  106.95  77.00 -30.00   58
 12  \w    152.00 178.00   1.00    1.20    --  106.95 125.00  90.00   26
 13  \w     50.00 110.00   1.00    1.20    --  106.95 -45.00   0.00   60
 14  \w     34.00  61.00   1.00    1.20    --  106.95-125.00 120.00   27
 15  \w     35.00 128.00   1.00    1.20    --  106.95 -61.00-150.00   93
 16  \w     61.00 107.00   1.00    1.20    --  106.95 -95.00-180.00   46
 17  \w     39.00  87.00   1.00    1.00    --   41.11-125.00-180.00   48
 18  \w   -106.00 -17.00   1.00    1.00    --  -41.11 -38.00 120.00   89
 19  \w    -68.00  -9.00   1.00    1.00    --  -41.23 -77.00 -60.00   59
 20  \w    -89.00 -29.00   1.00    1.00    --  -41.23 -77.00 -90.00   60
 21  \w     19.00  48.00   1.00    1.00    --   41.23  57.00 -30.00   29
 22  \w     19.00  47.00   1.00    1.00    --   41.23  57.00-120.00   28
 23  \w     24.00  67.00   1.00    1.00    --   41.23  38.00 -90.00   43
 24  \w     78.00 104.00   1.00    1.20    --  106.95  61.00 -30.00   26
 25  \w     78.00 104.00   1.00    1.20    --  106.95  61.00-120.00   26
 26  \w     74.00  99.00   1.00    1.20    --  106.95  77.00 -60.00   25
 27  \w     74.00  99.00   1.00    1.20    --  106.95  77.00 -30.00   25
 28  \w     78.00 103.00   1.00    1.20    --  106.95  61.00 -60.00   25
 29  \w     74.00  99.00   1.00    1.20    --  106.95  77.00 -90.00   25
 30  \w     74.00  99.00   1.00    1.20    --  106.95  77.00-120.00   25
 31  \w     78.00 103.00   1.00    1.20    --  106.95  61.00 -90.00   25
 32  \w     83.00 109.00   1.00    1.20    --  106.95  45.00 -30.00   26
 33  \w     82.00 108.00   1.00    1.20    --  106.95  45.00 -60.00   26
 34  \w     81.00 106.00   1.00    1.20    --  106.95  45.00-120.00   25
 35  \w     81.00 107.00   1.00    1.20    --  106.95  45.00   0.00   26
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0844552000
_diffrn_orient_matrix_UB_12      0.0091995000
_diffrn_orient_matrix_UB_13      0.0244176000
_diffrn_orient_matrix_UB_21      0.0446109000
_diffrn_orient_matrix_UB_22      -0.0470664000
_diffrn_orient_matrix_UB_23      0.0728264000
_diffrn_orient_matrix_UB_31      0.0161158000
_diffrn_orient_matrix_UB_32      0.1784243000
_diffrn_orient_matrix_UB_33      0.0179215000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0418
_diffrn_reflns_av_unetI/netI     0.0398
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.978
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            26400
_diffrn_reflns_point_group_measured_fraction_full 0.952
_diffrn_reflns_point_group_measured_fraction_max 0.926
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.601
_diffrn_reflns_theta_min         2.262
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.895
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.71033
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43f (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.282
_exptl_crystal_description       block
_exptl_crystal_F_000             1072
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.11
_refine_diff_density_max         0.607
_refine_diff_density_min         -0.398
_refine_diff_density_rms         0.078
_refine_ls_abs_structure_details
;
 Flack x determined using 3692 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.11(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.030
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     657
_refine_ls_number_reflns         9894
_refine_ls_number_restraints     13
_refine_ls_restrained_S_all      1.033
_refine_ls_R_factor_all          0.0703
_refine_ls_R_factor_gt           0.0670
_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^)+(0.1361P)^2^+1.3325P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1879
_refine_ls_wR_factor_ref         0.1941
_reflns_Friedel_coverage         0.766
_reflns_Friedel_fraction_full    0.896
_reflns_Friedel_fraction_max     0.866
_reflns_number_gt                9283
_reflns_number_total             9894
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            np9b00247_si_003.cif
_cod_data_source_block           s134_2
_cod_database_code               1552590
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.908
_shelx_estimated_absorpt_t_min   0.893
_reflns_odcompleteness_completeness 100.00
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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. Uiso/Uaniso restraints and constraints
Uanis(O11W) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
Uanis(O12W) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
3.a Ternary CH refined with riding coordinates:
 C7'(H7'), C1(H1), C018(H018), C01C(H01C), C01D(H01D), C9(H9)
3.b Secondary CH2 refined with riding coordinates:
 C00W(H00A,H00B), C8'(H8'A,H8'B), C9'(H9'A,H9'B), C4(H4A,H4B), C01L(H01J,H01K),
  C01N(H01L,H01M), C01Q(H01N,H01O), C3(H3A,H3B)
3.c Aromatic/amide H refined with riding coordinates:
 C8(H8), C00O(H00O), C5(H5), C012(H012), C3'(H3'), C015(H015), C2'(H2'),
 C01F(H01F)
3.d Idealised Me refined as rotating group:
 C10'(H10A,H10B,H10C), C01I(H01A,H01B,H01E), C01J(H01G,H01H,H01I), C11(H11A,
 H11B,H11C), C10(H10D,H10E,H10F), C12(H12A,H12B,H12C), C01U(H01P,H01Q,H01R),
 C01W(H01S,H01T,H01U)
;
_olex2_date_sample_data_collection 2018-09-28
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.370
_oxdiff_exptl_absorpt_empirical_full_min 0.710