Desymmetrization of Cyclopropenes via the Potassium-Templated Diastereoselective 7- exo- trig Cycloaddition of Tethered Amino Alcohols toward Enantiopure Cyclopropane-Fused Oxazepanones with Antimycobacterial Activity.
Maslivetc, Vladimir A.; Turner, Danielle N.; McNair, Kimberly N.; Frolova, Liliya; Rogelj, Snezna; Maslivetc, Anna A.; Aksenov, Nicolai A.; Rubina, Marina; Rubin, Michael; The Journal of organic chemistry 83 (2018) 5650–5664; doi:10.1021/acs.joc.8b00640

data_4034781
_publ_section_title
;
 Desymmetrization of Cyclopropenes via the Potassium-Templated
 Diastereoselective 7- exo- trig Cycloaddition of Tethered Amino Alcohols
 toward Enantiopure Cyclopropane-Fused Oxazepanones with Antimycobacterial
 Activity.
;
_journal_issue                   10
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              5650
_journal_page_last               5664
_journal_paper_doi               10.1021/acs.joc.8b00640
_journal_volume                  83
_journal_year                    2018
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C20 H19 Cl2 N O2'
_chemical_formula_sum            'C20 H19 Cl2 N O2'
_chemical_formula_weight         376.26
_chemical_name_systematic
(1S,3R,4S,7S)-7-(2,4-dichlorophenyl)-4,5-dimethyl-3-phenyl-2-oxa-5-azabicyclo[5.1.0]octan-6-one
_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
_audit_creation_date             2017-11-09
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5337)
;
_cell_angle_alpha                90
_cell_angle_beta                 110.687(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   16.0106(4)
_cell_length_b                   6.60080(10)
_cell_length_c                   18.1470(4)
_cell_measurement_reflns_used    23916
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      75.9980
_cell_measurement_theta_min      5.1830
_cell_volume                     1794.17(7)
_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      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2529
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.949
_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    -68.00  31.00   0.50    1.00    --  -41.35  51.00 139.00  198
  2  \w   -114.00 -14.00   0.50    1.00    --  -41.35 -51.00  -6.00  200
  3  \w     14.00 114.00   0.50    1.00    --   41.35  51.00 139.00  200
  4  \w     85.00 178.00   0.50    4.00    --  112.00  51.00 139.00  186
  5  \w     40.00 139.00   0.50    4.00    --  112.00 -51.00  -6.00  198
  6  \w     -1.00  26.00   0.50    1.00    --   38.00  94.00 106.19   54
  7  \w      1.00  82.00   0.50    1.00    --   41.35 -99.00-150.00  162
  8  \w     17.00 116.00   0.50    1.00    --   41.35  38.00-120.00  198
  9  \w     23.00  97.00   0.50    1.00    --   41.35-125.00 -30.00  148
 10  \w     17.00  46.00   0.50    1.00    --   50.00  80.00 165.48   58
 11  \w     20.00  46.00   0.50    1.00    --   54.00  81.00 -69.28   52
 12  \w     21.00  47.00   0.50    1.00    --   54.00  79.00-109.84   52
 13  \w     38.00 142.00   0.50    1.00    --   70.00  75.00 -71.01  208
 14  \w     79.00 160.00   0.50    4.00    --  112.00  77.00-120.00  162
 15  \w    130.00 177.00   0.50    4.00    --  112.00  77.00 -90.00   94
 16  \w    115.00 141.00   0.50    4.00    --  112.00 111.00  30.00   52
 17  \w     79.00 104.00   0.50    4.00    --  112.00  77.00-150.00   50
 18  \w    116.00 175.00   0.50    4.00    --  112.00  77.00-150.00  118
 19  \w     39.00  88.00   0.50    4.00    --  112.00 -95.00-180.00   98
 20  \w     91.00 116.00   0.50    4.00    --  112.00-111.00  30.00   50
 21  \w     80.00 106.00   0.50    4.00    --  112.00  77.00 -90.00   52
 22  \w    121.00 177.00   0.50    4.00    --  112.00 111.00 150.00  112
 23  \w     58.00 150.00   0.50    4.00    --  112.00 178.00  60.00  184
 24  \w    107.00 146.00   0.50    4.00    --  112.00 111.00   0.00   78
 25  \w     85.00 111.00   0.50    4.00    --  112.00  61.00 -90.00   52
 26  \w     89.00 174.00   0.50    4.00    --  112.00  30.00   0.00  170
 27  \w     87.00 113.00   0.50    4.00    --  112.00  61.00-120.00   52
 28  \w     75.00 102.00   0.50    4.00    --  112.00 178.00   0.00   54
 29  \w    107.00 148.00   0.50    4.00    --  112.00 178.00   0.00   82
 30  \w     79.00 178.00   0.50    4.00    --  112.00  77.00-180.00  198
 31  \w     87.00 113.00   0.50    4.00    --  112.00  45.00-120.00   52
 32  \w     88.00 114.00   0.50    4.00    --  112.00  45.00  30.00   52
 33  \w    152.00 178.00   0.50    4.00    --  112.00  45.00  30.00   52
 34  \w     87.00 159.00   0.50    4.00    --  112.00  45.00  90.00  144
 35  \w    129.00 155.00   0.50    4.00    --  112.00  45.00-180.00   52
 36  \w     87.00 152.00   0.50    4.00    --  112.00  45.00 -60.00  130
 37  \w    131.00 159.00   0.50    4.00    --  112.00  30.00-120.00   56
 38  \w    132.00 167.00   0.50    4.00    --  112.00 111.00  60.00   70
 39  \w     70.00  97.00   0.50    1.00    --   41.85-125.00 -90.00   54
 40  \w    103.00 130.00   0.50    4.00    --  112.00 111.00-180.00   54
 41  \w     88.00 114.00   0.50    4.00    --  112.00  45.00 -90.00   52
 42  \w     92.00 118.00   0.50    4.00    --  112.00  61.00 -60.00   52
 43  \w     27.00  60.00   0.50    4.00    --  112.00   0.00  30.00   66
 44  \w    150.00 176.00   0.50    4.00    --  112.00   0.00  30.00   52
 45  \w     39.00  65.00   0.50    4.00    --  112.00-111.00-120.00   52
 46  \w     83.00 109.00   0.50    4.00    --  112.00  61.00 -90.00   52
 47  \w    136.00 169.00   0.50    4.00    --  112.00 111.00-120.00   66
 48  \w     88.00 114.00   0.50    4.00    --  112.00-111.00-150.00   52
 49  \w    -89.00 -64.00   0.50    1.00    --  -41.85 -51.00  -5.00   50
 50  \w     20.00  46.00   0.50    1.00    --   54.00  81.00  -2.92   52
 51  \w     20.00  46.00   0.50    1.00    --   54.00  81.00-148.84   52
 52  \w     33.00 142.00   0.50    1.00    --   66.00  77.00  54.23  218
 53  \w     38.00 146.00   0.50    1.00    --   70.00  76.00 137.41  216
 54  \w    -44.00 -19.00   0.50    1.00    --  -41.85  51.00 140.00   50
 55  \w     36.00  62.00   0.50    4.00    --  112.00 -95.00 150.00   52
 56  \w     83.00 109.00   0.50    4.00    --  112.00  61.00-120.00   52
 57  \w    111.00 137.00   0.50    4.00    --  112.00 111.00 -30.00   52
 58  \w     40.00  65.00   0.50    1.00    --   41.60  51.00 139.00   50
 59  \w     79.00 105.00   0.50    4.00    --  112.00  77.00 -90.00   52
 60  \w    105.00 131.00   0.50    4.00    --  112.00 111.00-120.00   52
 61  \w     20.00  46.00   0.50    1.00    --   54.00  81.00 108.75   52
 62  \w     20.00  46.00   0.50    1.00    --   54.00  81.00  39.98   52
 63  \w     20.00  46.00   0.50    1.00    --   54.00  81.00 132.73   52
 64  \w     30.00 138.00   0.50    1.00    --   62.00  76.00-164.44  216
 65  \w     34.00 142.00   0.50    1.00    --   66.00  76.00   1.19  216
 66  \w     34.00 111.00   0.50    1.00    --   66.00  76.00-113.81  154
 67  \w     37.00 146.00   0.50    1.00    --   70.00  77.00 113.35  218
 68  \w     41.00  66.00   0.50    1.00    --   42.35  51.00 139.00   50
 69  \w     62.00  99.00   0.50    4.00    --  112.00 178.00-180.00   74
 70  \w    137.00 163.00   0.50    4.00    --  112.00 111.00 -90.00   52
 71  \w    135.00 172.00   0.50    4.00    --  112.00 111.00-120.00   74
 72  \w    -89.00 -64.00   0.50    1.00    --  -41.60 -51.00  -5.00   50
 73  \w     62.00  89.00   0.50    1.00    --   41.60-125.00  90.00   54
 74  \w     40.00  65.00   0.50    1.00    --   41.60  51.00 139.00   50
 75  \w    -43.00 -18.00   0.50    1.00    --  -41.60  51.00 139.00   50
 76  \w   -114.00 -22.00   0.50    1.00    --  -41.60 -57.00 120.00  184
 77  \w     65.00  90.00   0.50    4.00    --  112.00 -51.00  -5.00   50
 78  \w     23.00  77.00   0.50    1.00    --   41.60-125.00  90.00  108
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0979617000
_diffrn_orient_matrix_UB_12      0.0565306000
_diffrn_orient_matrix_UB_13      -0.0460756000
_diffrn_orient_matrix_UB_21      0.0301310000
_diffrn_orient_matrix_UB_22      0.1339489000
_diffrn_orient_matrix_UB_23      -0.0555687000
_diffrn_orient_matrix_UB_31      -0.0082260000
_diffrn_orient_matrix_UB_32      -0.1826135000
_diffrn_orient_matrix_UB_33      -0.0549855000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0598
_diffrn_reflns_av_unetI/netI     0.0305
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.949
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            37549
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.947
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.484
_diffrn_reflns_theta_min         4.575
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.360
_exptl_absorpt_correction_T_max  0.606
_exptl_absorpt_correction_T_min  0.343
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
Analytical numeric absorption correction using a multifaceted crystal
			model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
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    1.393
_exptl_crystal_description       irregular
_exptl_crystal_F_000             784
_exptl_crystal_size_max          0.429
_exptl_crystal_size_mid          0.373
_exptl_crystal_size_min          0.244
_refine_diff_density_max         0.463
_refine_diff_density_min         -0.361
_refine_diff_density_rms         0.073
_refine_ls_abs_structure_details
;
 Flack x determined using 3122 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.003(9)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.085
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     432
_refine_ls_number_reflns         7296
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.085
_refine_ls_R_factor_all          0.0521
_refine_ls_R_factor_gt           0.0509
_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^)+(0.0718P)^2^+2.3595P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1394
_refine_ls_wR_factor_ref         0.1417
_reflns_Friedel_coverage         0.833
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.945
_reflns_number_gt                7158
_reflns_number_total             7296
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo8b00640_si_002.cif
_cod_data_source_block           anna_29092017_vm311_85_cryo
_cod_database_code               4034781
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         C20H19Cl2NO
_reflns_odcompleteness_completeness 99.93
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.9849(9)
 0.0151(9)
2. 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
3.a Ternary CH refined with riding coordinates:
 C6(H6), C10(H10), C5(H5), C3(H3), C4(H4), C11(H11)
3.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C7(H7A,H7B)
3.c Aromatic/amide H refined with riding coordinates:
 C35(H35), C36(H36), C37(H37), C38(H38), C39(H39), C21(H21), C26(H26),
 C23(H23), C25(H25), C18(H18), C20(H20), C33(H33), C32(H32), C31(H31), C30(H30),
  C29(H29)
3.d Fitted hexagon refined as free rotating group:
 C34(C35,C36,C37,C38,C39), C28(C33,C32,C31,C30,C29)
3.e Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C13(H13A,H13B,H13C), C15(H15A,H15B,H15C), C12(H12A,H12B,
 H12C)
;
_shelx_res_checksum              361
_shelx_hkl_checksum              68459
_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 1.947
_oxdiff_exptl_absorpt_empirical_full_min 0.541