A Concise, Efficient and Scalable Total Synthesis of Thapsigargin and Nortrilobolide from (R)-(-)-Carvone.
Chen, Dezhi; Evans, P. Andrew; Journal of the American Chemical Society 139 (2017) 6046–6049; doi:10.1021/jacs.7b01734

data_4126104
_publ_section_title
;
 A Concise, Efficient and Scalable Total Synthesis of Thapsigargin and
 Nortrilobolide from (R)-(-)-Carvone.
;
_journal_issue                   17
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              6046
_journal_page_last               6049
_journal_paper_doi               10.1021/jacs.7b01734
_journal_volume                  139
_journal_year                    2017
_chemical_formula_moiety         'C31 H50 O7 Si2'
_chemical_formula_sum            'C31 H50 O7 Si2'
_chemical_formula_weight         590.89
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method           'manual editing of SHELXL-2014/7 template'
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.161(2)
_cell_length_b                   11.489(2)
_cell_length_c                   30.374(6)
_cell_measurement_reflns_used    9958
_cell_measurement_temperature    180(2)
_cell_measurement_theta_max      25.31
_cell_measurement_theta_min      2.70
_cell_volume                     3545.9(12)
_computing_cell_refinement
' Saint V8.34A and SADABS V2012/1 (Apex2, v2013.10-0; Bruker AXS)'
_computing_data_collection
' APEX2 software package v2013.10-0 (Bruker AXS)'
_computing_data_reduction
' Saint V8.34A and SADABS V2012/1 (Apex2, v2013.10-0; Bruker AXS)'
_computing_molecular_graphics    ' XP (SHELXTL-NT v6.14, Bruker AXS)'
_computing_publication_material
;
;
_computing_structure_refinement  ' SHELXL-2014/7 (Sheldrick, 2014)'
_computing_structure_solution    ' SHELXT-2014 (Sheldrick, 2014)'
_diffrn_ambient_temperature      180(2)
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.994
_diffrn_measurement_device_type  'Bruker Smart Apex2 CCD (Bruker AXS)'
_diffrn_measurement_method       'CCD rotation images,\f and \w scans'
_diffrn_radiation_monochromator  'horizontal mounted graphite crystal'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0261
_diffrn_reflns_av_unetI/netI     0.0304
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       38
_diffrn_reflns_limit_l_min       -38
_diffrn_reflns_number            30155
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.059
_diffrn_reflns_theta_min         1.341
_diffrn_source                   'Bruker AXS K780, fine-focus sealed tube'
_exptl_absorpt_coefficient_mu    0.139
_exptl_absorpt_correction_T_max  0.7455
_exptl_absorpt_correction_T_min  0.7192
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SADABS v2012/1 (Apex2, Bruker AXS)'
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.107
_exptl_crystal_description       plate-like
_exptl_crystal_F_000             1280
_exptl_crystal_size_max          0.150
_exptl_crystal_size_mid          0.150
_exptl_crystal_size_min          0.150
_refine_diff_density_max         0.463
_refine_diff_density_min         -0.230
_refine_diff_density_rms         0.038
_refine_ls_abs_structure_details
;
 Flack x determined using 2348 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.03(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.030
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     474
_refine_ls_number_reflns         7731
_refine_ls_number_restraints     468
_refine_ls_restrained_S_all      1.025
_refine_ls_R_factor_all          0.0540
_refine_ls_R_factor_gt           0.0410
_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^)+(0.0532P)^2^+0.5060P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0980
_refine_ls_wR_factor_ref         0.1056
_reflns_Friedel_coverage         0.780
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.992
_reflns_number_gt                6366
_reflns_number_total             7731
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b01734_si_002.cif
_cod_data_source_block           DY001_a
_cod_original_cell_volume        3545.8(12)
_cod_database_code               4126104
_shelx_estimated_absorpt_t_min   0.979
_shelx_estimated_absorpt_t_max   0.979
_shelx_res_checksum              42396
_shelx_hkl_checksum              99297