Asymmetric Induction via a Helically Chiral Anion: Enantioselective Pentacarboxycyclopentadiene Brønsted Acid-Catalyzed Inverse-Electron-Demand Diels-Alder Cycloaddition of Oxocarbenium Ions.
Gheewala, Chirag D.; Hirschi, Jennifer S.; Lee, Wai-Hang; Paley, Daniel W.; Vetticatt, Mathew J.; Lambert, Tristan H.; Journal of the American Chemical Society 140 (2018) 3523–3527; doi:10.1021/jacs.8b00260

data_4132018
_publ_section_title
;
 Asymmetric Induction via a Helically Chiral Anion: Enantioselective
 Pentacarboxycyclopentadiene Br\/onsted Acid-Catalyzed
 Inverse-Electron-Demand Diels-Alder Cycloaddition of Oxocarbenium Ions.
;
_journal_issue                   10
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              3523
_journal_page_last               3527
_journal_paper_doi               10.1021/jacs.8b00260
_journal_volume                  140
_journal_year                    2018
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C13 H16 O3'
_chemical_formula_sum            'C13 H16 O3'
_chemical_formula_weight         220.26
_space_group_crystal_system      orthorhombic
_space_group_IT_number           18
_space_group_name_Hall           'P 2 2ab'
_space_group_name_H-M_alt        'P 21 21 2'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2017-06-30
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5337)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   28.7833(4)
_cell_length_b                   7.66350(10)
_cell_length_c                   5.26380(10)
_cell_measurement_reflns_used    11647
_cell_measurement_temperature    100.0(2)
_cell_measurement_theta_max      72.7070
_cell_measurement_theta_min      5.9460
_cell_volume                     1161.09(3)
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.0(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.0549
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.996
_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    -64.00  30.00   1.00    1.00    --  -37.66  77.00 150.00   94
  2  \w   -106.00 -20.00   1.00    1.00    --  -37.66 -42.00  -2.99   86
  3  \w     57.00 110.00   1.00    1.00    --   37.66 178.00   0.00   53
  4  \w     57.00 110.00   1.00    1.00    --   37.66 178.00 -90.00   53
  5  \w     93.00 178.00   1.00    5.00    --  111.00  61.00-150.00   85
  6  \w     42.00 109.00   1.00    5.00    --  111.00 -94.00 -90.00   67
  7  \w     42.00 109.00   1.00    5.00    --  111.00 -94.00  90.00   67
  8  \w     44.00 129.00   1.00    5.00    --  111.00 -61.00   0.00   85
  9  \w     90.00 178.00   1.00    5.00    --  111.00  30.00 -30.00   88
 10  \w     93.00 178.00   1.00    5.00    --  111.00  61.00  90.00   85
 11  \w     84.00 178.00   1.00    5.00    --  111.00  77.00-120.00   94
 12  \w     84.00 178.00   1.00    5.00    --  111.00  77.00 -30.00   94
 13  \w     42.00 109.00   1.00    5.00    --  111.00 -94.00  30.00   67
 14  \w     90.00 178.00   1.00    5.00    --  111.00  30.00  90.00   88
 15  \w    100.00 178.00   1.00    5.00    --  111.00 111.00 120.00   78
 16  \w     42.00 109.00   1.00    5.00    --  111.00 -94.00 150.00   67
 17  \w     42.00 109.00   1.00    5.00    --  111.00 -94.00-180.00   67
 18  \w     41.00 116.00   1.00    5.00    --  111.00-111.00 -30.00   75
 19  \w     93.00 178.00   1.00    5.00    --  111.00  61.00   0.00   85
 20  \w   -105.00 -21.00   1.00    1.00    --  -37.66 -57.00 -90.00   84
 21  \w   -105.00 -21.00   1.00    1.00    --  -37.66 -57.00  90.00   84
 22  \w   -105.00 -21.00   1.00    1.00    --  -37.66 -57.00-180.00   84
 23  \w     57.00 110.00   1.00    1.00    --   37.66 178.00 120.00   53
 24  \w     94.00 178.00   1.00    5.00    --  111.00  45.00-120.00   84
 25  \w     84.00 178.00   1.00    5.00    --  111.00  77.00 -90.00   94
 26  \w     93.00 178.00   1.00    5.00    --  111.00  61.00  30.00   85
 27  \w     84.00 178.00   1.00    5.00    --  111.00  77.00 -60.00   94
 28  \w     90.00 178.00   1.00    5.00    --  111.00  30.00-180.00   88
 29  \w     84.00 178.00   1.00    5.00    --  111.00  77.00  60.00   94
 30  \w     84.00 178.00   1.00    5.00    --  111.00  77.00-180.00   94
 31  \w     84.00 178.00   1.00    5.00    --  111.00  77.00   0.00   94
 32  \w     90.00 178.00   1.00    5.00    --  111.00  30.00-150.00   88
 33  \w     84.00 178.00   1.00    5.00    --  111.00  77.00  30.00   94
 34  \w     94.00 178.00   1.00    5.00    --  111.00  45.00 120.00   84
 35  \w     93.00 178.00   1.00    5.00    --  111.00  61.00 120.00   85
 36  \w    -54.00  30.00   1.00    1.00    --  -37.66  57.00 -30.00   84
 37  \w   -110.00 -34.00   1.00    1.00    --  -37.66 178.00 -30.00   76
 38  \w   -105.00 -11.00   1.00    1.00    --  -37.66 -77.00   0.00   94
 39  \w      5.00  33.00   1.00    1.00    --   37.66  88.00 -78.19   28
 40  \w     41.00 116.00   1.00    5.00    --  111.00-111.00   0.00   75
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0439858000
_diffrn_orient_matrix_UB_12      0.0517750000
_diffrn_orient_matrix_UB_13      -0.1486825000
_diffrn_orient_matrix_UB_21      -0.0305067000
_diffrn_orient_matrix_UB_22      0.0732272000
_diffrn_orient_matrix_UB_23      -0.2156372000
_diffrn_orient_matrix_UB_31      -0.0002807000
_diffrn_orient_matrix_UB_32      0.1797760000
_diffrn_orient_matrix_UB_33      0.1308831000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0363
_diffrn_reflns_av_unetI/netI     0.0184
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       35
_diffrn_reflns_limit_h_min       -35
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       6
_diffrn_reflns_limit_l_min       -6
_diffrn_reflns_number            19062
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.124
_diffrn_reflns_theta_min         5.975
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.720
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.814
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
Numerical absorption correction based on gaussian integration over
			a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.260
_exptl_crystal_description       irregular
_exptl_crystal_F_000             472
_exptl_crystal_size_max          0.143
_exptl_crystal_size_mid          0.106
_exptl_crystal_size_min          0.076
_refine_diff_density_max         0.150
_refine_diff_density_min         -0.150
_refine_diff_density_rms         0.033
_refine_ls_abs_structure_details
;
 Flack x determined using 916 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.05(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.081
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     147
_refine_ls_number_reflns         2330
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.081
_refine_ls_R_factor_all          0.0280
_refine_ls_R_factor_gt           0.0276
_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^)+(0.0306P)^2^+0.3291P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0694
_refine_ls_wR_factor_ref         0.0699
_reflns_Friedel_coverage         0.660
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.995
_reflns_number_gt                2307
_reflns_number_total             2330
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b00260_si_005.cif
_cod_data_source_block           chirag6
_cod_database_code               4132018
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'C13 H16 O3'
_reflns_odcompleteness_completeness 98.62
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     73.59
_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
2.a Ternary CH refined with riding coordinates:
 C10(H10), C13(H13)
2.b Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B), C15(H15A,H15B)
2.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C6(H6)
2.d Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), C16(H16A,H16B,H16C)
;
_shelx_res_checksum              1693
_shelx_hkl_checksum              30478
_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 1.612
_oxdiff_exptl_absorpt_empirical_full_min 0.677