Asymmetric Ring-Opening of Donor–Acceptor Cyclopropanes with Primary Arylamines Catalyzed by a Chiral Heterobimetallic Catalyst
Luo, Weiwei; Sun, Zhicheng; Fernando, E. H. Nisala; Nesterov, Vladimir N.; Cundari, Thomas R.; Wang, Hong; ACS Catalysis 9 (2019) 8285–; doi:10.1021/acscatal.9b02523

data_4514814
_publ_section_title
;
 Asymmetric Ring-Opening of Donor--Acceptor Cyclopropanes with Primary
 Arylamines Catalyzed by a Chiral Heterobimetallic Catalyst
;
_journal_issue                   9
_journal_name_full               'ACS Catalysis'
_journal_page_first              8285
_journal_paper_doi               10.1021/acscatal.9b02523
_journal_volume                  9
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C20 H23 N O5'
_chemical_formula_sum            'C20 H23 N O5'
_chemical_formula_weight         357.39
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2018-08-02
_audit_creation_method
;
Olex2 1.2-ac3
(compiled 2017.01.05 svn.r3372 for Rigaku Oxford Diffraction, GUI svn.r5289)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   5.78428(3)
_cell_length_b                   12.07053(5)
_cell_length_c                   25.84988(10)
_cell_measurement_reflns_used    49523
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      76.4110
_cell_measurement_theta_min      3.4110
_cell_volume                     1804.821(14)
_computing_cell_refinement       'CrysAlisPro 1.171.40.12b (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.40.12b (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.40.12b (Rigaku OD, 2018)'
_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    'XT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.992
_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     16.00  41.00   0.50    5.00    --   38.00  74.00  40.40   50
  2  \w     31.00  57.00   0.50    5.00    --   47.20  57.00  30.00   52
  3  \w     35.00 114.00   0.50    5.00    --   47.20  19.00  30.00  158
  4  \w     86.00 113.00   0.50    5.00    --   47.20  57.00  30.00   54
  5  \w     84.00 123.00   0.50    5.00    --   54.00  65.00  98.61   78
  6  \w     75.00 101.00   0.50    5.00    --   47.20  63.00 160.53   52
  7  \w     35.00  61.00   0.50    5.00    --   50.00  66.00  41.08   52
  8  \w     36.00  74.00   0.50    5.00    --   54.00  65.00  98.61   76
  9  \w     30.00  56.00   0.50    5.00    --   47.20  63.00 160.53   52
 10  \w     42.00  75.00   0.50    5.00    --   62.00  69.00  96.95   66
 11  \w     38.00  79.00   0.50    5.00    --   58.00  67.00  71.82   82
 12  \w     92.00 178.00   0.50    0.50    --  105.24  61.00 -30.00  172
 13  \w    140.00 172.00   0.50    0.50    --  105.24  61.00 -90.00   64
 14  \w    146.00 172.00   0.50    0.50    --  105.24  77.00-150.00   52
 15  \w    113.00 138.00   0.50    0.50    --  105.24 116.00 -60.00   50
 16  \w     97.00 174.00   0.50    0.50    --  105.24  61.00-120.00  154
 17  \w     91.00 145.00   0.50    0.50    --  105.24  77.00-150.00  108
 18  \w     89.00 137.00   0.50    0.50    --  105.24  77.00-180.00   96
 19  \w     91.00 134.00   0.50    0.50    --  105.24  61.00 -90.00   86
 20  \w    101.00 154.00   0.50    0.50    --  105.24  45.00 -60.00  106
 21  \w     85.00 137.00   0.50    0.50    --  105.24  77.00 -30.00  104
 22  \w     89.00 178.00   0.50    0.50    --  105.24  61.00   0.00  178
 23  \w    131.00 178.00   0.50    0.50    --  105.24  77.00  90.00   94
 24  \w    127.00 153.00   0.50    0.50    --  105.24  61.00  60.00   52
 25  \w     93.00 178.00   0.50    0.50    --  105.24  61.00 150.00  170
 26  \w     90.00 115.00   0.50    0.50    --  105.24 163.00  88.00   50
 27  \w     71.00 119.00   0.50    5.00    --   47.20 163.00  88.00   96
 28  \w     51.00  88.00   0.50    5.00    --   70.00  67.00 -51.01   74
 29  \w     92.00 176.00   0.50    0.50    --  105.24  61.00  30.00  168
 30  \w     93.00 178.00   0.50    0.50    --  105.24  30.00 120.00  170
 31  \w     86.00 118.00   0.50    0.50    --  105.24  77.00  90.00   64
 32  \w     89.00 119.00   0.50    0.50    --  105.24  61.00  60.00   60
 33  \w     39.00 110.00   0.50    5.00    --   58.00  67.00-101.91  142
 34  \w     72.00 106.00   0.50    5.00    --   47.20  19.00-180.00   68
 35  \w     36.00  61.00   0.50    5.00    --   47.20  19.00-180.00   50
 36  \w     34.00  62.00   0.50    5.00    --   47.20  57.00-120.00   56
 37  \w     32.00  57.00   0.50    5.00    --   47.20  57.00-150.00   50
 38  \w     38.00  63.00   0.50    5.00    --   58.00  67.00-117.61   50
 39  \w     26.00  94.00   0.50    5.00    --   42.00  68.00 -54.99  136
 40  \w     92.00 157.00   0.50    0.50    --  105.24  61.00-150.00  130
 41  \w     57.00 100.00   0.50    0.50    --  105.24 -94.00-150.00   86
 42  \w     47.00 112.00   0.50    0.50    --  105.24-116.00-149.00  130
 43  \w     43.00 120.00   0.50    0.50    --  105.24 -61.00-180.00  154
 44  \w     27.00  91.00   0.50    5.00    --   47.20-116.00-149.00  128
 45  \w     32.00 109.00   0.50    0.50    --  105.24 -94.00 -30.00  154
 46  \w     74.00 110.00   0.50    0.50    --  105.24 -94.00  30.00   72
 47  \w     97.00 122.00   0.50    0.50    --  105.24-163.00  62.00   50
 48  \w     89.00 114.00   0.50    5.00    --   47.20-163.00  62.00   50
 49  \w     32.00  98.00   0.50    0.50    --  105.24 -94.00 150.00  132
 50  \w     42.00  67.00   0.50    0.50    --  105.24 -94.00  30.00   50
 51  \w     32.00 128.00   0.50    0.50    --  105.24 -77.00  30.00  192
 52  \w     36.00  63.00   0.50    0.50    --  105.24 -45.00-120.00   54
 53  \w     15.00  41.00   0.50    5.00    --   38.00  75.00  68.63   52
 54  \w     15.00  40.00   0.50    5.00    --   38.00  76.00  12.51   50
 55  \w     14.00  39.00   0.50    5.00    --   38.00  78.00 -24.38   50
 56  \w    -13.00  12.00   0.50    5.00    --   22.00 101.00  51.64   50
 57  \w    -11.00  19.00   0.50    5.00    --   22.00  97.00 104.21   60
 58  \w     -7.00  18.00   0.50    5.00    --   26.00  97.00 161.88   50
 59  \w     30.00  56.00   0.50    0.50    --  105.24 -30.00 120.00   52
 60  \w     30.00  58.00   0.50    0.50    --  105.24 -30.00  60.00   56
 61  \w    -11.00  14.00   0.50    5.00    --   22.00  96.00-102.72   50
 62  \w    -13.00  16.00   0.50    5.00    --   22.00 100.00-152.91   58
 63  \w    -69.00 -44.00   0.50    5.00    --  -47.20 116.00 -60.00   50
 64  \w    -73.00 -14.00   0.50    0.50    --  -86.25 116.00 -60.00  118
 65  \w    -76.00 -51.00   0.50    0.50    --  -86.25 163.00  88.00   50
 66  \w   -101.00 -55.00   0.50    5.00    --  -47.20 163.00  88.00   92
 67  \w   -113.00 -87.00   0.50    0.50    --  -86.25 163.00  88.00   52
 68  \w    -82.00 -56.00   0.50    0.50    --  -70.00 -58.00   5.19   52
 69  \w    -78.00 -51.00   0.50    0.50    --  -70.00 -68.00 -53.00   54
 70  \w    -81.00 -51.00   0.50    0.50    --  -70.00 -67.00 -77.80   60
 71  \w    -84.00 -59.00   0.50    0.50    --  -78.00 -65.00 -31.72   50
 72  \w    -81.00 -56.00   0.50    0.50    --  -74.00 -63.00  33.39   50
 73  \w    -86.00 -60.00   0.50    0.50    --  -74.00 -57.00 108.39   52
 74  \w    -81.00 -55.00   0.50    0.50    --  -74.00 -68.00 158.25   52
 75  \w    -79.00 -51.00   0.50    0.50    --  -70.00 -65.00 174.19   56
 76  \w    -85.00 -59.00   0.50    0.50    --  -78.00 -65.00 175.03   52
 77  \w   -103.00 -68.00   0.50    0.50    --  -82.00 -57.00 135.51   70
 78  \w    -89.00 -63.00   0.50    0.50    --  -74.00 -55.00  81.07   52
 79  \w    -94.00 -69.00   0.50    0.50    --  -86.25 -61.00  36.28   50
 80  \w    -91.00 -66.00   0.50    0.50    --  -86.00 -67.00  -7.57   50
 81  \w    -93.00 -67.00   0.50    0.50    --  -82.00 -61.00 -55.30   52
 82  \w    -93.00 -68.00   0.50    0.50    --  -86.25 -64.00 -66.84   50
 83  \w    -95.00 -70.00   0.50    0.50    --  -86.25 -62.00-105.11   50
 84  \w    -91.00 -65.00   0.50    0.50    --  -82.00 -59.00-155.96   52
 85  \w    -92.00 -67.00   0.50    0.50    --  -86.25 -65.00-113.35   50
 86  \w    -96.00 -71.00   0.50    0.50    --  -86.25 -61.00 -97.34   50
 87  \w    -95.00 -68.00   0.50    0.50    --  -86.25 -68.00 -80.44   54
 88  \w    -91.00 -66.00   0.50    0.50    --  -86.00 -67.00-121.39   50
 89  \w    -93.00 -68.00   0.50    0.50    --  -86.25 -66.00-151.84   50
 90  \w   -106.00 -81.00   0.50    5.00    --  -47.20-116.00-149.00   50
 91  \w    -95.00 -70.00   0.50    0.50    --  -86.25 -69.00  58.74   50
 92  \w    -94.00 -69.00   0.50    0.50    --  -86.25 -61.00 106.65   50
 93  \w    -95.00 -70.00   0.50    0.50    --  -86.25 -60.00  79.06   50
 94  \w    -95.00 -70.00   0.50    0.50    --  -86.25 -69.00  42.44   50
 95  \w    -94.00 -69.00   0.50    0.50    --  -86.25 -61.00   0.00   50
 96  \w    -94.00 -69.00   0.50    0.50    --  -86.25 -61.00  21.24   50
 97  \w   -112.00 -66.00   0.50    0.50    --  -86.25 -68.00 -23.77   92
 98  \w    -94.00 -69.00   0.50    0.50    --  -86.25 -61.00  90.00   50
 99  \w    -93.00 -68.00   0.50    0.50    --  -86.25 -63.00 141.22   50
100  \w    -97.00 -69.00   0.50    0.50    --  -86.25 -60.00 160.59   56
101  \w   -125.00 -66.00   0.50    0.50    --  -86.25 -68.00 128.32  118
102  \w   -116.00 -69.00   0.50    0.50    --  -86.25 -65.00  73.34   94
103  \w   -105.00 -80.00   0.50    5.00    --  -47.20-163.00  62.00   50
104  \w   -120.00 -95.00   0.50    0.50    --  -86.25-163.00  62.00   50
105  \w   -159.00-134.00   0.50    0.50    --  -86.25 -64.00 -66.84   50
106  \w   -159.00-133.00   0.50    0.50    --  -86.25 -61.00 -97.34   52
107  \w   -149.00-124.00   0.50    0.50    --  -86.25 -65.00-113.35   50
108  \w   -142.00-117.00   0.50    0.50    --  -86.25 -66.00-151.84   50
109  \w   -113.00 -69.00   0.50    0.50    --  -86.25 -67.00-161.46   88
110  \w   -142.00-117.00   0.50    0.50    --  -86.25-116.00-149.00   50
111  \w   -156.00-130.00   0.50    0.50    --  -86.25 -62.00-105.11   52
112  \w   -156.00-112.00   0.50    0.50    --  -86.25 -68.00 -80.44   88
113  \w   -153.00-127.00   0.50    0.50    --  -86.25 -61.00  90.00   52
114  \w   -157.00-131.00   0.50    0.50    --  -86.25 -60.00 160.59   52
115  \w   -158.00-133.00   0.50    0.50    --  -86.25 -63.00 141.22   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0537061000
_diffrn_orient_matrix_UB_12      -0.1207738000
_diffrn_orient_matrix_UB_13      -0.0150778000
_diffrn_orient_matrix_UB_21      -0.0547957000
_diffrn_orient_matrix_UB_22      0.0270026000
_diffrn_orient_matrix_UB_23      -0.0569541000
_diffrn_orient_matrix_UB_31      0.2549715000
_diffrn_orient_matrix_UB_32      0.0312343000
_diffrn_orient_matrix_UB_33      -0.0090644000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0265
_diffrn_reflns_av_unetI/netI     0.0085
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            53639
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.989
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.494
_diffrn_reflns_theta_min         3.419
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.777
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.88440
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.12b (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear intense colourless'
_exptl_crystal_density_diffrn    1.315
_exptl_crystal_description       block
_exptl_crystal_F_000             760
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.062
_exptl_crystal_size_min          0.054
_refine_diff_density_max         0.188
_refine_diff_density_min         -0.133
_refine_diff_density_rms         0.029
_refine_ls_abs_structure_details
;
 Flack x determined using 1495 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.02(2)
_refine_ls_extinction_coef       0.0034(5)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.053
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     243
_refine_ls_number_reflns         3648
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.053
_refine_ls_R_factor_all          0.0232
_refine_ls_R_factor_gt           0.0229
_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^)+(0.0313P)^2^+0.3503P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0592
_refine_ls_wR_factor_ref         0.0594
_reflns_Friedel_coverage         0.703
_reflns_Friedel_fraction_full    0.997
_reflns_Friedel_fraction_max     0.984
_reflns_number_gt                3631
_reflns_number_total             3648
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs9b02523_si_003.cif
_cod_data_source_block           str0063lt100k
_cod_database_code               4514814
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C20H23NO5
_diffrn_oxdiff_ac3_digest_frames
;
01f3420aaeb41ecba762fee3797f7a83e000026a153
;
_diffrn_oxdiff_ac3_digest_hkl
;
014f1871ef3978a2c3a9ed808e0c5d7c2bf1f8
;
_reflns_odcompleteness_completeness 99.48
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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:
 C1(H1A), C3(H3)
2.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B)
2.c Aromatic/amide H refined with riding coordinates:
 C9(H9), C10(H10), C11(H11), C12(H12), C13(H13), C15(H15), C16(H16), C18(H18),
 C19(H19)
2.d Idealised Me refined as rotating group:
 C6(H6A,H6B,H6C), C7(H7A,H7B,H7C), C20(H20A,H20B,H20C)
;
_shelx_res_checksum              21365
_shelx_hkl_checksum              97213
_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 1.398
_oxdiff_exptl_absorpt_empirical_full_min 0.805