Total Synthesis of Pactamycin and Pactamycate: A Detailed Account
Stephen Hanessian; Ramkrishna Reddy Vakiti; Stéphane Dorich; Shyamapada Banerjee; Benoît Deschênes-Simard; Journal of Organic Chemistry 77 (2012) 9458–9472; doi:10.1021/jo301638z

data_4027642
_publ_section_title
;
 Total Synthesis of Pactamycin and Pactamycate: A Detailed Account
;
_journal_name_full               'Journal of Organic Chemistry'
_journal_page_first              9458
_journal_page_last               9472
_journal_paper_doi               10.1021/jo301638z
_journal_volume                  77
_journal_year                    2012
_chemical_absolute_configuration rmad
_chemical_compound_source        'Synthesized by the authors. See text'
_chemical_formula_moiety         'C33 H38 N4 O5 Si'
_chemical_formula_sum            'C33 H38 N4 O5 Si'
_chemical_formula_weight         598.76
_space_group_IT_number           5
_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_Hall  'C 2y'
_symmetry_space_group_name_H-M   'C 1 2 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-97
_cell_angle_alpha                90.00
_cell_angle_beta                 103.955(2)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   17.8975(7)
_cell_length_b                   7.3027(3)
_cell_length_c                   28.5293(11)
_cell_measurement_reflns_used    13265
_cell_measurement_temperature    150
_cell_measurement_theta_max      72.01
_cell_measurement_theta_min      3.19
_cell_volume                     3618.7(3)
_computing_cell_refinement       'SAINT V7.60A(Bruker AXS, 2008)'
_computing_data_collection       'APEX2  (Bruker AXS, 2008)'
_computing_data_reduction        'SAINT V7.60A(Bruker AXS, 2008)'
_computing_molecular_graphics    'SHELXTL v6.12 (Bruker AXS, 2001)'
_computing_publication_material  'UdMX (Maris, 2004)'
_computing_structure_refinement  'SHELXL97 (Sheldrick, 2008)'
_computing_structure_solution    'SHELXS97 (Sheldrick, 2008)'
_diffrn_ambient_temperature      150
_diffrn_detector_area_resol_mean 5.5
_diffrn_measured_fraction_theta_full 0.956
_diffrn_measured_fraction_theta_max 0.956
_diffrn_measurement_device_type  'Bruker Smart 6000'
_diffrn_measurement_method       \w
_diffrn_radiation_monochromator  'Helios optics'
_diffrn_radiation_source         'Rotating Anode'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.045
_diffrn_reflns_av_sigmaI/netI    0.0426
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_limit_l_min       -35
_diffrn_reflns_number            22572
_diffrn_reflns_theta_full        72.43
_diffrn_reflns_theta_max         72.43
_diffrn_reflns_theta_min         1.60
_exptl_absorpt_coefficient_mu    0.903
_exptl_absorpt_correction_T_max  0.8973
_exptl_absorpt_correction_T_min  0.6820
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'Sadabs (Sheldrick, 2004)'
_exptl_crystal_colour            Colorless
_exptl_crystal_density_diffrn    1.099
_exptl_crystal_description       block
_exptl_crystal_F_000             1272
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.12
_platon_squeeze_details
;
The crystal structure has been squeezed out with PLATON to remove high 
disordered ethyl acetate contribution from its solvate structure. 
PLATON found a total of 535.5 A^3 solvent accessible void volume with 
contribution from 194 electrons per cell. More precisely, there are two 
voids of 133 A^3 with 48 electrons contribution and two voids of 133 A^3 
with 49 electrons contribution estimated to contain ethyl acetate used as 
crystallization solvent.
Considering the solvent the physical data should be:
Formula moiety: 'C33 H38 N4 O5 Si, C4 H8 O2'
Density: 1.261 g cm-3
Absorption coefficient: 1.011 mm-1
F000: 1464.0
;
_refine_diff_density_max         1.341
_refine_diff_density_min         -0.228
_refine_diff_density_rms         0.068
_refine_ls_abs_structure_details 'Flack H D (1983), 2803 Friedel Pairs'
_refine_ls_abs_structure_Flack   0.16(3)
_refine_ls_extinction_coef       0.00095(15)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     SHELXL
_refine_ls_goodness_of_fit_ref   1.048
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     441
_refine_ls_number_reflns         6683
_refine_ls_number_restraints     193
_refine_ls_restrained_S_all      1.039
_refine_ls_R_factor_all          0.0643
_refine_ls_R_factor_gt           0.0612
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.1207P)^2^+0.9548P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1641
_refine_ls_wR_factor_ref         0.1676
_reflns_number_gt                6135
_reflns_number_total             6683
_reflns_threshold_expression     I>2\s(I)
_cod_data_source_file            jo301638z_si_009.cif
_cod_data_source_block           bent51
_cod_original_cell_volume        3618.7(2)
_cod_database_code               4027642