Enantioselective N-heterocyclic carbene-catalyzed nucleophilic dearomatization of alkyl pyridiniums
Flanigan, Darrin M.; Rovis, Tomislav; Chem. Sci.  (2017) –; doi:10.1039/C7SC02648J

data_1546754
_publ_section_title
;
 Enantioselective N-heterocyclic carbene-catalyzed nucleophilic
 dearomatization of alkyl pyridiniums
;
_journal_name_full               'Chem. Sci.'
_journal_paper_doi               10.1039/C7SC02648J
_journal_year                    2017
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C26 H32 N2 O3'
_chemical_formula_sum            'C26 H32 N2 O3'
_chemical_formula_weight         420.53
_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     dual
_audit_creation_date             2017-02-06
_audit_creation_method
;
Olex2 1.2
(compiled 2017.01.04 svn.r3372 for OlexSys, GUI svn.r5292)
;
_audit_update_record
;
2017-06-12 deposited with the CCDC.
2017-07-24 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   6.27180(10)
_cell_length_b                   14.71860(10)
_cell_length_c                   24.2813(2)
_cell_measurement_reflns_used    22641
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      72.9430
_cell_measurement_theta_min      4.6900
_cell_volume                     2241.46(4)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43 (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      100.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.0549
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.998
_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    -38.00 -11.00   1.00    4.00    --  -36.44 -77.00 120.00   27
  2  \w    -47.00 -18.00   1.00    4.00    --  -36.44 -77.00  90.00   29
  3  \w    -56.00 -10.00   1.00    4.00    --  -36.44 -77.00  30.00   46
  4  \w    -53.00 -18.00   1.00    4.00    --  -36.44 -37.00 -30.00   35
  5  \w    -46.00 -11.00   1.00    4.00    --  -36.44 -77.00 -60.00   35
  6  \w    -55.00 -10.00   1.00    4.00    --  -36.44 -77.00-120.00   45
  7  \w    -48.00 -10.00   1.00    4.00    --  -36.44 -77.00-180.00   38
  8  \w     31.00  74.00   1.00    4.00    --   36.44 -99.00 -60.00   43
  9  \w     88.00 116.00   1.00   20.00    --  111.00-111.00 -30.00   28
 10  \w     87.00 115.00   1.00   20.00    --  111.00-111.00-120.00   28
 11  \w     82.00 132.00   1.00   20.00    --  111.00 -69.00-138.27   50
 12  \w     73.00 107.00   1.00   20.00    --  111.00  15.00 -60.00   34
 13  \w     90.00 116.00   1.00   20.00    --  111.00  30.00 -90.00   26
 14  \w     94.00 120.00   1.00   20.00    --  111.00  59.00 -93.50   26
 15  \w    125.00 174.00   1.00   20.00    --  111.00  59.00 -93.50   49
 16  \w    142.00 168.00   1.00   20.00    --  111.00  77.00-120.00   26
 17  \w    136.00 176.00   1.00   20.00    --  111.00  77.00-150.00   40
 18  \w    141.00 177.00   1.00   20.00    --  111.00  30.00-120.00   36
 19  \w    142.00 168.00   1.00   20.00    --  111.00  33.00-160.88   26
 20  \w    134.00 159.00   1.00   20.00    --  111.00  30.00 -90.00   25
 21  \w    123.00 176.00   1.00   20.00    --  111.00  77.00 -60.00   53
 22  \w    148.00 174.00   1.00   20.00    --  111.00  77.00  30.00   26
 23  \w    148.00 178.00   1.00   20.00    --  111.00  61.00  60.00   30
 24  \w    144.00 170.00   1.00   20.00    --  111.00  61.00  90.00   26
 25  \w    140.00 166.00   1.00   20.00    --  111.00  30.00  60.00   26
 26  \w    131.00 157.00   1.00   20.00    --  111.00  77.00 120.00   26
 27  \w    146.00 172.00   1.00   20.00    --  111.00  77.00 150.00   26
 28  \w    135.00 177.00   1.00   20.00    --  111.00  30.00 150.00   42
 29  \w    125.00 178.00   1.00   20.00    --  111.00  73.00 107.72   53
 30  \w    127.00 172.00   1.00   20.00    --  111.00  77.00   0.00   45
 31  \w    129.00 155.00   1.00   20.00    --  111.00  30.00  30.00   26
 32  \w    123.00 164.00   1.00   20.00    --  111.00  30.00   0.00   41
 33  \w    123.00 148.00   1.00   20.00    --  111.00  72.00 102.00   25
 34  \w    114.00 152.00   1.00   20.00    --  111.00  15.00 120.00   38
 35  \w     92.00 119.00   1.00   20.00    --  111.00  30.00  60.00   27
 36  \w     93.00 119.00   1.00   20.00    --  111.00  61.00  60.00   26
 37  \w     94.00 119.00   1.00   20.00    --  111.00  61.00  90.00   25
 38  \w     84.00 115.00   1.00   20.00    --  111.00  77.00  30.00   31
 39  \w     93.00 143.00   1.00   20.00    --  111.00  61.00  30.00   50
 40  \w     90.00 123.00   1.00   20.00    --  111.00  30.00  30.00   33
 41  \w     90.00 118.00   1.00   20.00    --  111.00  30.00   0.00   28
 42  \w     93.00 119.00   1.00   20.00    --  111.00  61.00 -30.00   26
 43  \w     93.00 119.00   1.00   20.00    --  111.00  61.00   0.00   26
 44  \w     84.00 112.00   1.00   20.00    --  111.00  77.00 -30.00   28
 45  \w     94.00 133.00   1.00   20.00    --  111.00  61.00 -60.00   39
 46  \w     93.00 118.00   1.00   20.00    --  111.00  61.00-120.00   25
 47  \w    131.00 166.00   1.00   20.00    --  111.00  70.00-161.09   35
 48  \w    127.00 177.00   1.00   20.00    --  111.00  61.00-180.00   50
 49  \w    128.00 154.00   1.00   20.00    --  111.00  30.00-180.00   26
 50  \w    114.00 171.00   1.00   20.00    --  111.00 111.00 -90.00   57
 51  \w     92.00 144.00   1.00   20.00    --  111.00  30.00-150.00   52
 52  \w     90.00 116.00   1.00   20.00    --  111.00  30.00-180.00   26
 53  \w     88.00 114.00   1.00   20.00    --  111.00  70.00-161.09   26
 54  \w     93.00 119.00   1.00   20.00    --  111.00  61.00-180.00   26
 55  \w     92.00 117.00   1.00   20.00    --  111.00  33.00-160.88   25
 56  \w     90.00 118.00   1.00   20.00    --  111.00  30.00-120.00   28
 57  \w     84.00 110.00   1.00   20.00    --  111.00  77.00-150.00   26
 58  \w     84.00 122.00   1.00   20.00    --  111.00  77.00-120.00   38
 59  \w     94.00 120.00   1.00   20.00    --  111.00  45.00 -60.00   26
 60  \w     90.00 122.00   1.00   20.00    --  111.00  30.00 -30.00   32
 61  \w     84.00 110.00   1.00   20.00    --  111.00  77.00 -60.00   26
 62  \w     84.00 135.00   1.00   20.00    --  111.00  77.00 -90.00   51
 63  \w     84.00 110.00   1.00   20.00    --  111.00  77.00   0.00   26
 64  \w     84.00 110.00   1.00   20.00    --  111.00  77.00  60.00   26
 65  \w     88.00 113.00   1.00   20.00    --  111.00  72.00 102.00   25
 66  \w     86.00 112.00   1.00   20.00    --  111.00  73.00 107.72   26
 67  \w     93.00 119.00   1.00   20.00    --  111.00  61.00 150.00   26
 68  \w     90.00 132.00   1.00   20.00    --  111.00  30.00 120.00   42
 69  \w     90.00 129.00   1.00   20.00    --  111.00  30.00 150.00   39
 70  \w     84.00 110.00   1.00   20.00    --  111.00  77.00 120.00   26
 71  \w     84.00 110.00   1.00   20.00    --  111.00  77.00  90.00   26
 72  \w     84.00 110.00   1.00   20.00    --  111.00  77.00 150.00   26
 73  \w     73.00 105.00   1.00   20.00    --  111.00  15.00 120.00   32
 74  \w     51.00 135.00   1.00   20.00    --  111.00 -25.00 102.41   84
 75  \w    112.00 137.00   1.00   20.00    --  111.00 -77.00  60.00   25
 76  \w     79.00 108.00   1.00   20.00    --  111.00 -94.00  60.00   29
 77  \w     72.00  98.00   1.00   20.00    --  111.00 -94.00 150.00   26
 78  \w     72.00 116.00   1.00   20.00    --  111.00-111.00 150.00   44
 79  \w     49.00  75.00   1.00   20.00    --  111.00 -94.00  60.00   26
 80  \w     42.00 116.00   1.00   20.00    --  111.00-111.00  60.00   74
 81  \w     43.00  94.00   1.00   20.00    --  111.00 -77.00  60.00   51
 82  \w     42.00  68.00   1.00   20.00    --  111.00 -94.00 150.00   26
 83  \w     19.00  75.00   1.00    4.00    --   36.44 -99.00 150.00   56
 84  \w     42.00  67.00   1.00   20.00    --  111.00-111.00 -30.00   25
 85  \w     44.00 102.00   1.00   20.00    --  111.00 -48.00-118.67   58
 86  \w     48.00  75.00   1.00   20.00    --  111.00 -69.00-138.27   27
 87  \w     45.00 115.00   1.00   20.00    --  111.00 -77.00-180.00   70
 88  \w     49.00  75.00   1.00   20.00    --  111.00-111.00-120.00   26
 89  \w     84.00 110.00   1.00   20.00    --  111.00  77.00-180.00   26
 90  \w     84.00 139.00   1.00   20.00    --  111.00 178.00  90.00   55
 91  \w     -5.00  31.00   1.00    4.00    --  -36.44  57.00-180.00   36
 92  \w    -52.00  30.00   1.00    4.00    --  -36.44  57.00 -90.00   82
 93  \w    -51.00  31.00   1.00    4.00    --  -36.44  57.00   0.00   82
 94  \w    -50.00 -24.00   1.00    4.00    --  -36.44  57.00-180.00   26
 95  \w    -93.00 -19.00   1.00    4.00    --  -36.44 -37.00-180.00   74
 96  \w   -100.00 -73.00   1.00    4.00    --  -36.44 -77.00 -60.00   27
 97  \w   -101.00 -14.00   1.00    4.00    --  -36.44 -72.00 -27.00   87
 98  \w    -74.00 -39.00   1.00    4.00    --  -36.44 -19.00   0.00   35
 99  \w   -103.00 -21.00   1.00    4.00    --  -36.44 -57.00 120.00   82
100  \w   -107.00 -82.00   1.00    4.00    --  -36.44 -19.00   0.00   25
101  \w   -103.00 -78.00   1.00    4.00    --  -36.44 -77.00 120.00   25
102  \w    -62.00  31.00   1.00    4.00    --  -36.44  77.00  60.00   93
103  \w    -64.00 -38.00   1.00    4.00    --  -36.44 178.00  60.00   26
104  \w   -109.00 -84.00   1.00    4.00    --  -36.44 178.00  60.00   25
;
_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      0.0376338000
_diffrn_orient_matrix_UB_12      -0.0789777000
_diffrn_orient_matrix_UB_13      0.0405034000
_diffrn_orient_matrix_UB_21      -0.2068175000
_diffrn_orient_matrix_UB_22      0.0249565000
_diffrn_orient_matrix_UB_23      0.0307075000
_diffrn_orient_matrix_UB_31      -0.1269996000
_diffrn_orient_matrix_UB_32      -0.0639666000
_diffrn_orient_matrix_UB_33      -0.0380042000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0424
_diffrn_reflns_av_unetI/netI     0.0200
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            43306
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.990
_diffrn_reflns_theta_min         3.511
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.645
_exptl_absorpt_correction_T_max  0.977
_exptl_absorpt_correction_T_min  0.910
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43 (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    1.246
_exptl_crystal_description       irregular
_exptl_crystal_F_000             904
_exptl_crystal_size_max          0.196
_exptl_crystal_size_mid          0.049
_exptl_crystal_size_min          0.048
_refine_diff_density_max         0.158
_refine_diff_density_min         -0.155
_refine_diff_density_rms         0.032
_refine_ls_abs_structure_details
;
 Flack x determined using 1817 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.07(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.045
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     282
_refine_ls_number_reflns         4462
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.045
_refine_ls_R_factor_all          0.0296
_refine_ls_R_factor_gt           0.0288
_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^)+(0.0405P)^2^+0.4725P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0737
_refine_ls_wR_factor_ref         0.0743
_reflns_Friedel_coverage         0.729
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.998
_reflns_number_gt                4366
_reflns_number_total             4462
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7sc02648j2.cif
_cod_data_source_block           bcorr_a
_cod_database_code               1546754
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'c26 h32 n2 o3'
_reflns_odcompleteness_completeness 97.49
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_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:
 C3(H3), C4(H4), C18(H18)
2.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C5(H5A,H5B), C6(H6A,H6B), C7(H7A,H7B), C19(H19A,H19B), C24(H24A,
 H24B), C25(H25A,H25B)
2.c Aromatic/amide H refined with riding coordinates:
 C9(H9), C10(H10), C12(H12), C13(H13), C27(H27), C28(H28), C29(H29), C30(H30),
 C31(H31)
2.d Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C), C23(H23A,H23B,H23C)
;
_shelx_res_checksum              31466
_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 1.424
_oxdiff_exptl_absorpt_empirical_full_min 0.667