Highly Stereoselective Synthesis of Fused Cyclopropane-γ-Lactams via Biocatalytic Iron-Catalyzed Intramolecular Cyclopropanation
Ren, Xinkun; Chandgude, Ajay L.; Fasan, Rudi; ACS Catalysis  (2020) 2308–2313; doi:10.1021/acscatal.9b05383

data_4517360
_publ_section_title
;
 Highly Stereoselective Synthesis of Fused Cyclopropane-\g-Lactams via
 Biocatalytic Iron-Catalyzed Intramolecular Cyclopropanation
;
_journal_name_full               'ACS Catalysis'
_journal_page_first              2308
_journal_page_last               2313
_journal_paper_doi               10.1021/acscatal.9b05383
_journal_year                    2020
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C12 H13 N O'
_chemical_formula_sum            'C12 H13 N O'
_chemical_formula_weight         187.23
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2019-08-22
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2019.04.23 svn.r3594 for Rigaku Oxford Diffraction, GUI svn.r5739)
;
_cell_angle_alpha                90
_cell_angle_beta                 90.739(3)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   5.6803(2)
_cell_length_b                   9.2798(3)
_cell_length_c                   9.3092(3)
_cell_measurement_reflns_used    3711
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      77.2080
_cell_measurement_theta_min      4.7830
_cell_volume                     490.67(3)
_computing_cell_refinement       'CrysAlisPro 1.171.40.58a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.58a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.58a (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015b)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015a)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.988
_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    -83.00 -47.00   0.50    0.10    --  -49.75 -30.00 -91.00   72
  2  \w    -75.00 -18.00   0.50    0.10    --  -49.75  98.00-102.00  114
  3  \w    -20.00   5.00   0.50    0.10    --   49.75 -30.00 -91.00   50
  4  \w     58.00  83.00   0.50    0.10    --   49.75  30.00  68.00   50
  5  \w   -143.00-118.00   0.50    0.39    --  -84.25-110.00  61.00   50
  6  \w    -72.00 -47.00   0.50    0.39    --  -84.25 110.00 157.00   50
  7  \w   -145.00-120.00   0.50    0.39    --  -84.25 -98.00 150.00   50
  8  \w     51.00  98.00   0.50    0.39    --  105.75 -98.00 150.00   94
  9  \w    108.00 158.00   0.50    0.39    --  105.75 110.00 157.00  100
 10  \w    111.00 176.00   0.50    0.39    --  105.75  30.00  68.00  130
 11  \w    122.00 147.00   0.50    0.39    --  105.75  98.00-102.00   50
 12  \w     43.00  70.00   0.50    0.10    --   49.75  57.00-180.00   54
 13  \w     43.00  80.00   0.50    0.10    --   49.75  38.00 150.00   74
 14  \w     41.00  75.00   0.50    0.10    --   49.75  57.00-150.00   68
 15  \w    -97.00 -72.00   0.50    0.39    --  -84.25 -61.00-180.00   50
 16  \w    -99.00 -72.00   0.50    0.39    --  -84.25 -58.00 165.36   54
 17  \w    -88.00 -63.00   0.50    0.39    --  -84.25 -77.00-180.00   50
 18  \w   -104.00 -75.00   0.50    0.39    --  -84.25 -61.00 150.00   58
 19  \w   -151.00-125.00   0.50    0.39    --  -84.25 -30.00 150.00   52
 20  \w     68.00  96.00   0.50    0.39    --  105.75-125.00 150.00   56
 21  \w     56.00  81.00   0.50    0.39    --  105.75 -77.00 -60.00   50
 22  \w     36.00  70.00   0.50    0.39    --  105.75 -61.00  30.00   68
 23  \w     90.00 122.00   0.50    0.39    --  105.75 -77.00 -60.00   64
 24  \w     95.00 133.00   0.50    0.39    --  105.75  61.00-180.00   76
 25  \w     94.00 125.00   0.50    0.39    --  105.75  77.00 150.00   62
 26  \w     94.00 142.00   0.50    0.39    --  105.75  61.00 150.00   96
 27  \w     90.00 130.00   0.50    0.39    --  105.75  77.00 120.00   80
 28  \w     43.00  69.00   0.50    0.39    --  105.75 -61.00-150.00   52
 29  \w     25.00  52.00   0.50    0.10    --   49.87-109.00  61.00   54
 30  \w     -3.00  24.00   0.50    0.10    --  -49.87  19.00  90.00   54
 31  \w     -5.00  20.00   0.50    0.10    --  -49.87  19.00   0.00   50
 32  \w   -112.00 -83.00   0.50    0.10    --  -49.87-125.00  30.00   58
 33  \w     -4.00  22.00   0.50    0.10    --  -49.87  19.00 120.00   52
 34  \w    -15.00  13.00   0.50    0.10    --   49.87 -19.00 150.00   56
 35  \w     56.00  81.00   0.50    0.10    --   49.87-109.00  61.00   50
 36  \w     46.00  72.00   0.50    0.10    --   49.87-125.00-180.00   52
 37  \w    -20.00   6.00   0.50    0.10    --   49.87 -19.00   0.00   52
 38  \w     37.00  67.00   0.50    0.39    --  105.75 -61.00  60.00   60
 39  \w     35.00  78.00   0.50    0.39    --  105.75-125.00-150.00   86
 40  \w     67.00 104.00   0.50    0.39    --  105.75 -94.00 -60.00   74
 41  \w     80.00 109.00   0.50    0.39    --  105.75-125.00-150.00   58
 42  \w     57.00 104.00   0.50    0.39    --  105.75 -94.00  90.00   94
 43  \w     72.00 105.00   0.50    0.39    --  105.75 -94.00-120.00   66
 44  \w    135.00 176.00   0.50    0.39    --  105.75  45.00-120.00   82
 45  \w     39.00  65.00   0.50    0.39    --  105.75-125.00-180.00   52
 46  \w     34.00  59.00   0.50    0.39    --  105.75-125.00  30.00   50
 47  \w     61.00  87.00   0.50    0.39    --  105.75 -94.00  60.00   52
 48  \w     35.00  64.00   0.50    0.39    --  105.75 -94.00 -60.00   58
 49  \w     79.00 106.00   0.50    0.39    --  105.75-125.00  30.00   54
 50  \w     35.00  64.00   0.50    0.39    --  105.75 -61.00  90.00   58
 51  \w     77.00 111.00   0.50    0.39    --  105.75-125.00-180.00   68
 52  \w     65.00 107.00   0.50    0.39    --  105.75-109.00  61.00   84
 53  \w     97.00 144.00   0.50    0.39    --  105.75  77.00-180.00   94
 54  \w     40.00  66.00   0.50    0.39    --  105.75 -61.00-120.00   52
 55  \w    141.00 166.00   0.50    0.39    --  105.75  30.00 -90.00   50
 56  \w    134.00 172.00   0.50    0.39    --  105.75  45.00   0.00   76
 57  \w     97.00 126.00   0.50    0.39    --  105.75  45.00   0.00   58
 58  \w     34.00  59.00   0.50    0.39    --  105.75 -61.00   0.00   50
 59  \w    101.00 137.00   0.50    0.39    --  105.75  30.00 -90.00   72
 60  \w     98.00 127.00   0.50    0.39    --  105.75  45.00-120.00   58
;
_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      -0.1085838000
_diffrn_orient_matrix_UB_12      -0.0535869000
_diffrn_orient_matrix_UB_13      -0.1428644000
_diffrn_orient_matrix_UB_21      0.0203034000
_diffrn_orient_matrix_UB_22      0.1529103000
_diffrn_orient_matrix_UB_23      -0.0628771000
_diffrn_orient_matrix_UB_31      0.2477946000
_diffrn_orient_matrix_UB_32      -0.0360347000
_diffrn_orient_matrix_UB_33      -0.0549801000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0666
_diffrn_reflns_av_unetI/netI     0.0588
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            7207
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.974
_diffrn_reflns_theta_full        74.504
_diffrn_reflns_theta_max         77.848
_diffrn_reflns_theta_min         4.751
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.638
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.61067
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.58a (Rigaku Oxford Diffraction, 2019)
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    1.267
_exptl_crystal_description       needle
_exptl_crystal_F_000             200
_exptl_crystal_size_max          0.145
_exptl_crystal_size_mid          0.066
_exptl_crystal_size_min          0.035
_refine_diff_density_max         0.156
_refine_diff_density_min         -0.220
_refine_diff_density_rms         0.042
_refine_ls_abs_structure_details
;
 Flack x determined using 778 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.3(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.057
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     128
_refine_ls_number_reflns         2033
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.056
_refine_ls_R_factor_all          0.0482
_refine_ls_R_factor_gt           0.0438
_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^)+(0.0664P)^2^+0.0396P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1144
_refine_ls_wR_factor_ref         0.1183
_reflns_Friedel_coverage         0.853
_reflns_Friedel_fraction_full    0.988
_reflns_Friedel_fraction_max     0.957
_reflns_number_gt                1854
_reflns_number_total             2033
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs9b05383_si_002.cif
_cod_data_source_block           fasac13
_cod_depositor_comments
'Adding full bibliography for 4517359--4517360.cif.'
_cod_database_code               4517360
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.978
_shelx_estimated_absorpt_t_min   0.913
_diffrn_oxdiff_digest_frames
;
010cda9f0a4ba1ba8acc932fe7dd8e8c9f01874095a
;
_diffrn_oxdiff_digest_hkl
;
018bbef581843999c6ae73f0ec2cee76346d83
;
_reflns_odcompleteness_completeness 99.91
_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:
 C1(H1), C2(H2), C3(H3)
2.b Secondary CH2 refined with riding coordinates:
 C4(H4A,H4B)
2.c Aromatic/amide H refined with riding coordinates:
 C7(H7), C8(H8), C9(H9), C10(H10), C11(H11)
2.d Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C)
;
_shelx_res_checksum              81384
_shelx_hkl_checksum              82585
_olex2_submission_original_sample_id fasac13
_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 2.041
_oxdiff_exptl_absorpt_empirical_full_min 0.541