Highly Functionalized Tricyclic Oxazinanones via Pairwise Oxidative Dearomatization and N-Hydroxycarbamate Dehydrogenation: Molecular Diversity Inspired by Tetrodotoxin.
Good, Steffen N.; Sharpe, Robert J.; Johnson, Jeffrey S.; Journal of the American Chemical Society 139 (2017) 12422–12425; doi:10.1021/jacs.7b07745

data_4131642
_publ_section_title
;
 Highly Functionalized Tricyclic Oxazinanones via Pairwise Oxidative
 Dearomatization and N-Hydroxycarbamate Dehydrogenation: Molecular
 Diversity Inspired by Tetrodotoxin.
;
_journal_issue                   36
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              12422
_journal_page_last               12425
_journal_paper_doi               10.1021/jacs.7b07745
_journal_volume                  139
_journal_year                    2017
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C33 H37 N O9 Si'
_chemical_formula_sum            'C33 H37 N O9 Si'
_chemical_formula_weight         619.72
_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     iterative
_audit_creation_date             2015-07-22
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_cell_angle_alpha                90
_cell_angle_beta                 98.492(15)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   8.7035(18)
_cell_length_b                   8.1115(19)
_cell_length_c                   21.516(5)
_cell_measurement_reflns_used    8712
_cell_measurement_temperature    100
_cell_measurement_theta_max      66.70
_cell_measurement_theta_min      4.16
_cell_volume                     1502.3(6)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_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    'olex2.solve (Bourhis et al., 2015)'
_diffrn_ambient_temperature      100
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0474
_diffrn_reflns_av_unetI/netI     0.0310
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            29703
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        66.698
_diffrn_reflns_theta_max         66.698
_diffrn_reflns_theta_min         2.076
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.181
_exptl_absorpt_correction_T_max  0.9633
_exptl_absorpt_correction_T_min  0.7829
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.0695 before and 0.0574 after correction.
The Ratio of minimum to maximum transmission is 0.8127.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.370
_exptl_crystal_description       plate
_exptl_crystal_F_000             656
_exptl_crystal_size_max          0.315
_exptl_crystal_size_mid          0.296
_exptl_crystal_size_min          0.042
_refine_diff_density_max         0.235
_refine_diff_density_min         -0.225
_refine_diff_density_rms         0.037
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.04(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.063
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     413
_refine_ls_number_reflns         5267
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.063
_refine_ls_R_factor_all          0.0325
_refine_ls_R_factor_gt           0.0295
_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^)+(0.0353P)^2^+0.2728P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0682
_refine_ls_wR_factor_ref         0.0698
_reflns_Friedel_coverage         0.855
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.999
_reflns_number_gt                4981
_reflns_number_total             5267
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b07745_si_004.cif
_cod_data_source_block           x1507006
_cod_database_code               4131642
_shelx_estimated_absorpt_t_max   0.952
_shelx_estimated_absorpt_t_min   0.707
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.96(3) 0.04(3)
2. 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
3.a Ternary CH refined with riding coordinates:
 C38(H38), C40(H40)
3.b Secondary CH2 refined with riding coordinates:
 C19(H19A,H19B), C24(H24A,H24B), C31(H31A,H31B), C42(H42A,H42B)
3.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C6(H6), C7(H7), C9(H9), C10(H10), C11(H11), C12(H12),
 C13(H13), C33(H33), C34(H34), C35(H35), C36(H36), C37(H37)
3.d Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C), C16(H16A,H16B,H16C), C17(H17A,H17B,H17C)
;
_shelx_res_checksum              34873
_shelx_hkl_checksum              28308
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'