Enantioselective Total Synthesis of (+)-Lysergol: A Formal anti-Carbopalladation/Heck Cascade as the Key Step
Milde, Bastian; Pawliczek, Martin; Jones, Peter G.; Werz, Daniel B.; Organic Letters  (2017) –; doi:10.1021/acs.orglett.7b00675

data_1545660
_publ_section_title
;
 Enantioselective Total Synthesis of (+)-Lysergol: A Formal
 anti-Carbopalladation/Heck Cascade as the Key Step
;
_journal_name_full               'Organic Letters'
_journal_paper_doi               10.1021/acs.orglett.7b00675
_journal_year                    2017
_chemical_absolute_configuration ad
_chemical_formula_sum            'C39 H44 Br N O6 S Si'
_chemical_formula_weight         762.81
_chemical_name_systematic
;
 ?
;
_space_group_IT_number           4
_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 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                 92.9646(12)
_cell_angle_gamma                90.00
_cell_formula_units_Z            2
_cell_length_a                   6.04388(8)
_cell_length_b                   22.18157(15)
_cell_length_c                   13.72525(15)
_cell_measurement_reflns_used    49260
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      75.9500
_cell_measurement_theta_min      3.7670
_cell_volume                     1837.58(3)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43c (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43c (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43c (Rigaku OD, 2015)'
_computing_molecular_graphics    'Siemens XP'
_computing_publication_material  SHELXL-97
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector_area_resol_mean 10.3543
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Oxford Diffraction Xcalibur, Atlas, Nova'
_diffrn_measurement_method       \w-scan
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0626
_diffrn_reflns_av_sigmaI/netI    0.0236
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            105118
_diffrn_reflns_theta_full        75.00
_diffrn_reflns_theta_max         76.34
_diffrn_reflns_theta_min         3.22
_diffrn_source                   'micro-focus sealed X-ray tube'
_exptl_absorpt_coefficient_mu    2.751
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.67680
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43c (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.379
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       lath
_exptl_crystal_F_000             796
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.10
_exptl_crystal_size_min          0.03
_platon_squeeze_details
;
 The final residual electron density showed a pattern of small peaks
 corresponding to a toluene molecule. This could be refined freely
 but showed high U values (possibly because of occupation factors
 < 1) and further peaks indicating disorder. Additionally, the
 methyl group seemed to be disordered over two mutually para
 positions.
 Because of the unsatisfactory refinement of the toluene, the
 program SQUEEZE (part of the PLATON suite; A. L. Spek, University
 of Utrecht, Netherlands) was used to remove mathematically the
 effects of the solvent.
 The formula, the values for the formula mass, and associated
 parameters are based on an idealized composition of one toluene
 per asymmetric unit.
;
_refine_diff_density_max         0.863
_refine_diff_density_min         -0.582
_refine_diff_density_rms         0.051
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   -0.011(12)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.016
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     386
_refine_ls_number_reflns         7682
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.016
_refine_ls_R_factor_all          0.0374
_refine_ls_R_factor_gt           0.0365
_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^)+(0.0585P)^2^+0.9904P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0956
_refine_ls_wR_factor_ref         0.0964
_reflns_number_gt                7508
_reflns_number_total             7682
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ol7b00675_si_002.cif
_cod_data_source_block           wiskas
_cod_depositor_comments
;
The following automatic conversions were performed:

'_exptl_crystal_density_meas' value 'not measured' was changed to '?'
- the value is perceived as not measured.

Automatic conversion script
Id: cif_fix_values 4973 2017-02-22 13:04:09Z antanas 
;
_cod_original_sg_symbol_H-M      'P 21'
_cod_database_code               1545660