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_4131641
_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_formula_moiety         '1(C14 H19 N O5)'
_chemical_formula_sum            'C14 H19 N O5'
_chemical_formula_weight         281.30
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2015-05-04
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_cell_angle_alpha                75.367(3)
_cell_angle_beta                 64.510(2)
_cell_angle_gamma                72.713(2)
_cell_formula_units_Z            4
_cell_length_a                   11.2220(5)
_cell_length_b                   11.5293(6)
_cell_length_c                   13.0311(7)
_cell_measurement_reflns_used    9910
_cell_measurement_temperature    100
_cell_measurement_theta_max      66.59
_cell_measurement_theta_min      3.80
_cell_volume                     1437.83(13)
_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 0.974
_diffrn_measured_fraction_theta_max 0.974
_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  0.0289
_diffrn_reflns_av_unetI/netI     0.0211
_diffrn_reflns_Laue_measured_fraction_full 0.974
_diffrn_reflns_Laue_measured_fraction_max 0.974
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            24688
_diffrn_reflns_point_group_measured_fraction_full 0.974
_diffrn_reflns_point_group_measured_fraction_max 0.974
_diffrn_reflns_theta_full        66.629
_diffrn_reflns_theta_max         66.629
_diffrn_reflns_theta_min         3.798
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.825
_exptl_absorpt_correction_T_max  0.9954
_exptl_absorpt_correction_T_min  0.8047
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.0707 before and 0.0506 after correction.
The Ratio of minimum to maximum transmission is 0.8084.
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    1.299
_exptl_crystal_description       plate
_exptl_crystal_F_000             600
_exptl_crystal_size_max          0.262
_exptl_crystal_size_mid          0.182
_exptl_crystal_size_min          0.036
_refine_diff_density_max         0.240
_refine_diff_density_min         -0.222
_refine_diff_density_rms         0.036
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.168
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     743
_refine_ls_number_reflns         4960
_refine_ls_number_restraints     698
_refine_ls_restrained_S_all      1.112
_refine_ls_R_factor_all          0.0548
_refine_ls_R_factor_gt           0.0486
_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^)+(0.0514P)^2^+0.7072P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1370
_refine_ls_wR_factor_ref         0.1413
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4283
_reflns_number_total             4960
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b07745_si_005.cif
_cod_data_source_block           x1504001
_cod_database_code               4131641
_shelx_estimated_absorpt_t_max   0.971
_shelx_estimated_absorpt_t_min   0.813
_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. Restrained distances
 C61-C63
 1.5 with sigma of 0.02
 C62-C61
 1.5 with sigma of 0.02
3. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Others
 Sof(C41)=Sof(C42)=Sof(H42A)=Sof(H42B)=Sof(H42C)=Sof(C43)=Sof(H43A)=Sof(H43B)=
 Sof(H43C)=Sof(C44)=Sof(H44A)=Sof(H44B)=Sof(H44C)=Sof(C46)=Sof(C50)=Sof(C51)=
 Sof(H51A)=Sof(H51B)=Sof(H51C)=Sof(C52)=Sof(C54)=Sof(C56)=Sof(H56A)=Sof(H56B)=
 Sof(C57)=Sof(C58)=Sof(H58A)=Sof(H58B)=Sof(H58C)=Sof(C59)=Sof(H59)=Sof(C60)=
 Sof(H60)=Sof(N48)=Sof(O45)=Sof(O47)=Sof(O49)=Sof(O53)=Sof(O55)=1-FVAR(1)
 Sof(C1)=Sof(C2)=Sof(H2A)=Sof(H2B)=Sof(H2C)=Sof(C3)=Sof(H3A)=Sof(H3B)=Sof(H3C)=
 Sof(C4)=Sof(H4A)=Sof(H4B)=Sof(H4C)=Sof(C6)=Sof(C9)=Sof(C10)=Sof(C11)=Sof(C13)=
 Sof(H13A)=Sof(H13B)=Sof(C14)=Sof(C15)=Sof(H15)=Sof(C16)=Sof(H16)=Sof(C17)=
 Sof(H17A)=Sof(H17B)=Sof(H17C)=Sof(C19)=Sof(H19A)=Sof(H19B)=Sof(H19C)=Sof(N7)=
 Sof(O5)=Sof(O8)=Sof(O12)=Sof(O18)=Sof(O20)=FVAR(1)
 Sof(C61)=Sof(C62)=Sof(H62A)=Sof(H62B)=Sof(H62C)=Sof(C63)=Sof(H63A)=Sof(H63B)=
 Sof(H63C)=Sof(C64)=Sof(H64A)=Sof(H64B)=Sof(H64C)=Sof(C66)=Sof(C70)=Sof(C71)=
 Sof(H71A)=Sof(H71B)=Sof(H71C)=Sof(C72)=Sof(C74)=Sof(C76)=Sof(H76A)=Sof(H76B)=
 Sof(C77)=Sof(C78)=Sof(H78A)=Sof(H78B)=Sof(H78C)=Sof(C79)=Sof(H79)=Sof(C80)=
 Sof(H80)=Sof(N68)=Sof(O65)=Sof(O67)=Sof(O69)=Sof(O73)=Sof(O75)=1-FVAR(2)
 Sof(C21)=Sof(C22)=Sof(H22A)=Sof(H22B)=Sof(H22C)=Sof(C23)=Sof(H23A)=Sof(H23B)=
 Sof(H23C)=Sof(C24)=Sof(H24A)=Sof(H24B)=Sof(H24C)=Sof(C26)=Sof(C29)=Sof(C30)=
 Sof(C31)=Sof(C33)=Sof(H33A)=Sof(H33B)=Sof(C34)=Sof(C35)=Sof(H35)=Sof(C36)=
 Sof(H36)=Sof(C37)=Sof(H37A)=Sof(H37B)=Sof(H37C)=Sof(C39)=Sof(H39A)=Sof(H39B)=
 Sof(H39C)=Sof(N27)=Sof(O25)=Sof(O28)=Sof(O32)=Sof(O38)=Sof(O40)=FVAR(2)
5.a Secondary CH2 refined with riding coordinates:
 C13(H13A,H13B), C33(H33A,H33B), C76(H76A,H76B), C56(H56A,H56B)
5.b Aromatic/amide H refined with riding coordinates:
 C15(H15), C16(H16), C35(H35), C36(H36), C79(H79), C80(H80), C59(H59), C60(H60)
5.c Idealised Me refined as rotating group:
 C2(H2A,H2B,H2C), C3(H3A,H3B,H3C), C4(H4A,H4B,H4C), C17(H17A,H17B,H17C),
 C19(H19A,H19B,H19C), C22(H22A,H22B,H22C), C23(H23A,H23B,H23C), C24(H24A,H24B,
 H24C), C37(H37A,H37B,H37C), C39(H39A,H39B,H39C), C62(H62A,H62B,H62C), C63(H63A,
 H63B,H63C), C64(H64A,H64B,H64C), C71(H71A,H71B,H71C), C78(H78A,H78B,H78C),
 C42(H42A,H42B,H42C), C43(H43A,H43B,H43C), C44(H44A,H44B,H44C), C51(H51A,H51B,
 H51C), C58(H58A,H58B,H58C)
;
_shelx_res_checksum              46839
_shelx_hkl_checksum              96318
_shelx_shelxl_version_number     2014/7
_olex2_submission_original_sample_id sg-dn2075
_olex2_submission_special_instructions 'No special instructions were received'