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_4516785
_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         '2(C25 H35 N O8), 2(C4 H10 O), 0.38(H2 O)'
_chemical_formula_sum            'C58 H90.76 N2 O18.38'
_chemical_formula_weight         1110.22
_chemical_name_common            6-AH-235
_chemical_name_systematic        6-AH-235
_space_group_crystal_system      trigonal
_space_group_IT_number           145
_space_group_name_Hall           'P 32'
_space_group_name_H-M_alt        'P 32'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2016-09-26
_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                120
_cell_formula_units_Z            3
_cell_length_a                   20.8804(7)
_cell_length_b                   20.8804(7)
_cell_length_c                   11.5639(5)
_cell_measurement_reflns_used    9871
_cell_measurement_temperature    100
_cell_measurement_theta_max      78.80
_cell_measurement_theta_min      4.23
_cell_volume                     4366.3(3)
_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      100
_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 0.995
_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  0.0649
_diffrn_reflns_av_unetI/netI     0.0380
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            77290
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.981
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         79.349
_diffrn_reflns_theta_min         4.234
_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    0.770
_exptl_absorpt_correction_T_max  0.7512
_exptl_absorpt_correction_T_min  0.7024
_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    1.267
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             1799
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.593
_refine_diff_density_min         -0.616
_refine_diff_density_rms         0.044
_refine_ls_abs_structure_details
;
 Flack x determined using 4748 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.07(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.023
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     760
_refine_ls_number_reflns         12410
_refine_ls_number_restraints     13
_refine_ls_restrained_S_all      1.023
_refine_ls_R_factor_all          0.0537
_refine_ls_R_factor_gt           0.0448
_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^)+(0.0568P)^2^+1.5230P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1071
_refine_ls_wR_factor_ref         0.1130
_reflns_Friedel_coverage         0.973
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.968
_reflns_number_gt                11020
_reflns_number_total             12410
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            oc6b00361_si_005.cif
_cod_data_source_block           p16334_hex_a
_cod_database_code               4516785
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, {H1A,H1B} of O11, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, {H11A,H11B} of O11, All O(H) groups
2. Restrained distances
 O2A-H2A = O2B-H2B = O5A-H5A = O5B-H5B = O6A-H6A = O6B-H6B = O7A-H7A = O7B-H7B
 = O8A-H8A = O8B-H8B
 0.84 with sigma of 0.02
 N1A-H1A = N1B-H1B
 0.88 with sigma of 0.02
3. Others
 Sof(O11)=Sof(H11A)=Sof(H11B)=FVAR(1)
4.a Free rotating group:
 O11(H1A,H1B,H11A,H11B)
4.b Ternary CH refined with riding coordinates:
 C9A(H9A), C13A(H13A), C10A(H10A), C3B(H3B), C3A(H3A), C4A(H4A), C13B(H13B),
 C4B(H4B), C10B(H10B), C9B(H9B)
4.c Secondary CH2 refined with riding coordinates:
 C14A(H14A,H14B), C8A(H8AA,H8AB), C14B(H14C,H14D), C7A(H7AA,H7AB), C7B(H7BA,
 H7BB), C27(H27A,H27B), C28(H28A,H28B), C8B(H8BA,H8BB), C31(H31A,H31B),
 C32(H32A,H32B)
4.d Aromatic/amide H refined with riding coordinates:
 C23B(H23B), C23A(H23A), C24A(H24A), C25A(H25A), C24B(H24B), C25B(H25B)
4.e Idealised Me refined as rotating group:
 C16B(H16D,H16E,H16F), C16A(H16A,H16B,H16C), C17A(H17A,H17B,H17C), C19A(H19A,
 H19B,H19C), C17B(H17D,H17E,H17F), C19B(H19D,H19E,H19F), C20A(H20A,H20B,H20C),
 C18B(H18D,H18E,H18F), C29(H29A,H29B,H29C), C18A(H18A,H18B,H18C), C26(H26A,H26B,
 H26C), C20B(H20D,H20E,H20F), C30(H30A,H30B,H30C), C33(H33A,H33B,H33C)
;
_shelx_res_checksum              42253
_shelx_hkl_checksum              83697
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'