Chemical Synthesis of (+)-Ryanodine and (+)-20-Deoxyspiganthine.
Xu, Chen; Han, Arthur; Virgil, Scott C.; Reisman, Sarah E.; ACS central science 3 (2017) 278–282; doi:10.1021/acscentsci.6b00361

data_4516784
_publ_section_title
;
 Chemical Synthesis of (+)-Ryanodine and (+)-20-Deoxyspiganthine.
;
_journal_issue                   4
_journal_name_full               'ACS central science'
_journal_page_first              278
_journal_page_last               282
_journal_paper_doi               10.1021/acscentsci.6b00361
_journal_volume                  3
_journal_year                    2017
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C25 H35 N O9, 2(C4 H10 O), H2 O'
_chemical_formula_sum            'C33 H57 N O12'
_chemical_formula_weight         659.79
_chemical_name_common            CX-10-076
_chemical_name_systematic        CX-10-076
_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   mixed
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2016-09-25
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.9374(3)
_cell_length_b                   11.9604(3)
_cell_length_c                   27.4814(7)
_cell_measurement_reflns_used    9851
_cell_measurement_temperature    200
_cell_measurement_theta_max      78.52
_cell_measurement_theta_min      3.22
_cell_volume                     3595.00(16)
_computing_cell_refinement       'SAINT v8.34A (Bruker-AXS, 2007)'
_computing_data_collection       'APEX2 v2014.11-0 (Bruker-AXS, 2014)'
_computing_data_reduction        'SAINT v8.34A (Bruker-AXS, 2007)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_structure_solution    'SHELXS-2013/1 (She ldrick, 2013)'
_diffrn_ambient_temperature      200
_diffrn_detector                 'CMOS Area Detector'
_diffrn_detector_area_resol_mean 10.24
_diffrn_detector_type            'Bruker PHOTON 100 CMOS'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device       '\k-geometry diffractometer'
_diffrn_measurement_device_type  'Bruker D8 VENTURE Kappa Duo PHOTON 100 CMOS'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  'multilayer mirrors'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0438
_diffrn_reflns_av_unetI/netI     0.0166
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       35
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            91317
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         79.361
_diffrn_reflns_theta_min         3.216
_diffrn_source                   'I\mS HB micro-focus sealed tube'
_diffrn_source_current           1
_diffrn_source_power             0.05
_diffrn_source_type              'Incoatech I\mS HB'
_diffrn_source_voltage           50
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.759
_exptl_absorpt_correction_T_max  0.7543
_exptl_absorpt_correction_T_min  0.6648
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SADABS-2014/5 (Sheldrick, 2014)'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.219
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             1432
_exptl_crystal_size_max          0.26
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.19
_refine_diff_density_max         0.588
_refine_diff_density_min         -0.333
_refine_diff_density_rms         0.041
_refine_ls_abs_structure_details
;
 Flack x determined using 3121 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.05(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.045
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     439
_refine_ls_number_reflns         7764
_refine_ls_number_restraints     9
_refine_ls_restrained_S_all      1.045
_refine_ls_R_factor_all          0.0411
_refine_ls_R_factor_gt           0.0389
_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^)+(0.0638P)^2^+0.9060P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1064
_refine_ls_wR_factor_ref         0.1083
_reflns_Friedel_coverage         0.781
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.992
_reflns_number_gt                7391
_reflns_number_total             7764
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            oc6b00361_si_004.cif
_cod_data_source_block           p16323_2_a
_cod_database_code               4516784
_shelx_estimated_absorpt_t_max   0.869
_shelx_estimated_absorpt_t_min   0.827
_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, All C(H,H,H,H,H,H,H,H,H,H,H) groups
2. Restrained distances
 H7-O7 = H8-O8 = H5-O5 = H6-O6 = H9-O9 = H2-O2
 0.84 with sigma of 0.02
 H12A-O12 = H12B-O12
 0.87 with sigma of 0.02
 N1-H1
 0.88 with sigma of 0.02
3. Others
 Fixed U11: O7(0.02047) O12(0.02307)
 Fixed U12: O7(-0.00208) O12(-0.00339)
 Fixed U13: O7(0.00283) O12(0.00043)
 Fixed U22: O7(0.04486) O12(0.05241)
 Fixed U23: O7(0.00317) O12(-0.00732)
 Fixed U33: O7(0.02783) O12(0.04513)
4.a Ternary CH refined with riding coordinates:
 C13(H13), C10(H10), C3(H3), C9(H9A)
4.b Secondary CH2 refined with riding coordinates:
 C14(H14A,H14B), C7(H7A,H7B), C8(H8A,H8B), C27(H27A,H27B), C28(H28A,H28B),
 C31(H31A,H31B), C32(H32A,H32B)
4.c Aromatic/amide H refined with riding coordinates:
 C23(H23), C25(H25), C24(H24)
4.d Idealised Me refined as rotating group:
 C16(H16A,H16B,H16C), C19(H19A,H19B,H19C), C17(H17A,H17B,H17C), C29(H29A,H29B,
 H29C), C20(H20A,H20B,H20C), C18(H18A,H18B,H18C), C26(H26A,H26B,H26C), C30(H30A,
 H30B,H30C), C33(H33A,H33B,H33C)
;
_shelx_res_checksum              74556
_shelx_hkl_checksum              11772
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'