Diastereoselective Desymmetrization of Prochiral Cyclopentenediones via Cycloaddition Reaction with N-Phenacylbenzothiazolium Bromides.
Chandra Sahoo, Subas; Joshi, Mayank; Chandra Pan, Subhas; The Journal of organic chemistry 82 (2017) 12763–12770; doi:10.1021/acs.joc.7b01964

data_4033028
_publ_section_title
;
 Diastereoselective Desymmetrization of Prochiral Cyclopentenediones via
 Cycloaddition Reaction with N-Phenacylbenzothiazolium Bromides.
;
_journal_issue                   23
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              12763
_journal_page_last               12770
_journal_paper_doi               10.1021/acs.joc.7b01964
_journal_volume                  82
_journal_year                    2017
_chemical_formula_moiety         'C29 H25 N O4 S'
_chemical_formula_sum            'C29 H25 N O4 S'
_chemical_formula_weight         483.56
_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     dual
_audit_creation_date             2017-06-12
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5337)
;
_cell_angle_alpha                105.770(3)
_cell_angle_beta                 110.274(3)
_cell_angle_gamma                90.739(3)
_cell_formula_units_Z            4
_cell_length_a                   12.2788(5)
_cell_length_b                   13.5044(5)
_cell_length_c                   15.3335(4)
_cell_measurement_reflns_used    11819
_cell_measurement_temperature    100.0(2)
_cell_measurement_theta_max      32.7500
_cell_measurement_theta_min      2.8100
_cell_volume                     2279.07(15)
_computing_cell_refinement       'CrysAlisPro 1.171.39.7f (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.7f (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.7f (Rigaku OD, 2015)'
_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    'XT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.0(2)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.800
_diffrn_measured_fraction_theta_max 0.716
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
--------------------------------------------------------------------------
  1  \w    -69.00 118.20   0.30   20.00    --   29.89  54.00-120.00  624
  2  \w    -69.00 118.20   0.30   20.00    --   29.89  54.00 -30.00  624
  3  \w    -69.00 118.20   0.30   20.00    --   29.89  54.00 -30.00  624
  4  \w    -69.00 118.20   0.30   20.00    --   29.89  54.00 120.00  624
  5  \w    -69.00  64.20   0.30   20.00    --   29.89  54.00  30.00  444
;
_diffrn_measurement_device       'two-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Mini (ROW)'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0349464000
_diffrn_orient_matrix_UB_12      0.0013571000
_diffrn_orient_matrix_UB_13      0.0481863000
_diffrn_orient_matrix_UB_21      0.0136369000
_diffrn_orient_matrix_UB_22      0.0543936000
_diffrn_orient_matrix_UB_23      0.0121655000
_diffrn_orient_matrix_UB_31      -0.0493876000
_diffrn_orient_matrix_UB_32      0.0077926000
_diffrn_orient_matrix_UB_33      0.0138860000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0516
_diffrn_reflns_av_unetI/netI     0.0683
_diffrn_reflns_Laue_measured_fraction_full 0.800
_diffrn_reflns_Laue_measured_fraction_max 0.716
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            38001
_diffrn_reflns_point_group_measured_fraction_full 0.800
_diffrn_reflns_point_group_measured_fraction_max 0.716
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         32.840
_diffrn_reflns_theta_min         2.579
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.181
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.79306
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.7f (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.409
_exptl_crystal_description       prism
_exptl_crystal_F_000             1016
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.905
_refine_diff_density_min         -0.469
_refine_diff_density_rms         0.081
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.970
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     635
_refine_ls_number_reflns         12165
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      0.970
_refine_ls_R_factor_all          0.0806
_refine_ls_R_factor_gt           0.0542
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1010P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1480
_refine_ls_wR_factor_ref         0.1576
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7773
_reflns_number_total             12165
_reflns_threshold_expression     'I > 2\s(I)'
_twin_special_details
;
Component 2 rotated by 179.9665\% 
 around [-0.00 1.00 -0.00] (reciprocal) or [0.13 0.96 0.26] (direct)
;
_cod_data_source_file            jo7b01964_si_003.cif
_cod_data_source_block           scs-p10-142-a-100k_twin1_hklf4
_cod_depositor_comments
'Adding full bibliography for 4033027--4033028.cif.'
_cod_database_code               4033028
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C29 H25 N1 O4 S1'
_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, All O(H) groups
2.a Ternary CH refined with riding coordinates:
 C00M(H00M), C00W(H00W), C00X(H00X), C014(H014), C015(H015), C01A(H01C)
2.b Secondary CH2 refined with riding coordinates:
 C00P(H00A,H00B), C013(H01A,H01B), C019(H01O,H01Q), C01J(H01F,H01J)
2.c Aromatic/amide H refined with riding coordinates:
 C00L(H00L), C00Q(H00Q), C00S(H00S), C00T(H00T), C00Y(H00Y), C00Z(H00Z),
 C010(H010), C018(H018), C01C(H01R), C01D(H01D), C01E(H01E), C01F(H01S),
 C01G(H01G), C01H(H01H), C01I(H01I), C01L(H01Z), C01M(H01M), C01N(H01),
 C01O(H0AA), C01P(H01P), C01Q(H1AA), C01R(H2AA), C01T(H01T), C01U(H3AA),
 C01V(H01V), C01W(H01W), C01X(H4AA), C01Y(H5AA)
2.d Idealised Me refined as rotating group:
 C01K(H01U,H01X,H01Y), C01S(H01K,H01L,H01N)
2.e Idealised tetrahedral OH refined as rotating group:
 O005(H005), O006(H006)
;
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.354
_oxdiff_exptl_absorpt_empirical_full_min 0.775
_oxdiff_twin_integration_method  simultaneous
_oxdiff_twin_items               2