Assembly of a Key Dienic Intermediate for Tetrodotoxin via a Machetti-DeSarlo Reaction
Jaclyn Chau; Sanjia Xu; Marco A. Ciufolini; Journal of Organic Chemistry 78 (2013) 11901–11910; doi:10.1021/jo401960p

data_4028801
_publ_section_title
;
 Assembly of a Key Dienic Intermediate for Tetrodotoxin via a
 Machetti-DeSarlo Reaction
;
_journal_name_full               'Journal of Organic Chemistry'
_journal_page_first              11901
_journal_page_last               11910
_journal_paper_doi               10.1021/jo401960p
_journal_volume                  78
_journal_year                    2013
_chemical_formula_moiety         'C32 H41 N O6 Si'
_chemical_formula_sum            'C32 H41 N O6 Si'
_chemical_formula_weight         563.75
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     heavy
_audit_creation_date             2013-03-13
_audit_creation_method
;
  Olex2 1.2
  (compiled Dec  5 2012 16:17:34, GUI svn.r4385)
;
_cell_angle_alpha                97.358(3)
_cell_angle_beta                 92.479(3)
_cell_angle_gamma                107.783(3)
_cell_formula_units_Z            2
_cell_length_a                   8.9300(5)
_cell_length_b                   12.8309(7)
_cell_length_c                   14.2483(8)
_cell_measurement_reflns_used    9958
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      30.06
_cell_measurement_theta_min      2.38
_cell_volume                     1535.89(15)
_computing_data_reduction        'SAINT v7.60A (Bruker, 2009)'
_computing_molecular_graphics
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_publication_material
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_structure_refinement
;
XL, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_computing_structure_solution
;
XS, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_diffrn_ambient_temperature      100.0
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0335
_diffrn_reflns_av_unetI/netI     0.0282
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            50817
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.079
_diffrn_reflns_theta_min         2.052
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.120
_exptl_absorpt_correction_T_max  0.982
_exptl_absorpt_correction_T_min  0.934
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.0530 before and 0.0461 after correction.
The Ratio of minimum to maximum transmission is 0.9516.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.219
_exptl_crystal_description       prism
_exptl_crystal_F_000             604
_exptl_crystal_size_max          0.35
_exptl_crystal_size_mid          0.24
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.381
_refine_diff_density_min         -0.304
_refine_diff_density_rms         0.048
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.033
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     369
_refine_ls_number_reflns         8981
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.033
_refine_ls_R_factor_all          0.0499
_refine_ls_R_factor_gt           0.0370
_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^)+(0.0422P)^2^+0.5736P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0900
_refine_ls_wR_factor_ref         0.0975
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7310
_reflns_number_total             8981
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo401960p_si_002.cif
_cod_data_source_block           mc051
_cod_database_code               4028801
_cod_database_fobs_code          4028801
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  H19 of C19, H21 of C21, H22 of C22, {H23A,H23B} of C23, H18 of C18, H17 of
  C17, H16 of C16, H15 of C15, H14 of C14, H13 of C13, H12 of C12, H10 of C10,
  H9 of C9, H8 of C8, H7 of C7, H6 of C6
 At 1.5 times of:
  {H25A,H25B,H25C} of C25, {H2A,H2B,H2C} of C2, {H27A,H27B,H27C} of C27,
  {H30A,H30B,H30C} of C30, {H31A,H31B,H31C} of C31, {H32A,H32B,H32C} of C32,
  {H4A,H4B,H4C} of C4, {H3A,H3B,H3C} of C3
2.a Ternary CH refined with riding coordinates:
 C17(H17)
2.b Secondary CH2 refined with riding coordinates:
 C23(H23A,H23B)
2.c Aromatic/amide H refined with riding coordinates:
 C6(H6), C7(H7), C8(H8), C9(H9), C10(H10), C12(H12), C13(H13), C14(H14),
 C15(H15), C16(H16), C18(H18), C19(H19), C21(H21), C22(H22)
2.d Idealised Me refined as rotating group:
 C2(H2A,H2B,H2C), C3(H3A,H3B,H3C), C4(H4A,H4B,H4C), C25(H25A,H25B,H25C),
 C27(H27A,H27B,H27C), C30(H30A,H30B,H30C), C31(H31A,H31B,H31C), C32(H32A,H32B,
 H32C)
;
_shelx_estimated_absorpt_t_max   0.982
_shelx_estimated_absorpt_t_min   0.959
_shelxl_version_number           2012-9