Rh(II)-Catalyzed Spirocyclization of α-Diazo Homophthalimides with Cyclic Ethers.
Guranova, Natalia I.; Dar'in, Dmitry; Kantin, Grigory; Novikov, Alexander S.; Bakulina, Olga; Krasavin, Mikhail; The Journal of organic chemistry 84 (2019) 4534–4542; doi:10.1021/acs.joc.9b00245

data_4034262
_publ_section_title
;
 Rh(II)-Catalyzed Spirocyclization of \a-Diazo Homophthalimides with
 Cyclic Ethers.
;
_journal_issue                   7
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              4534
_journal_page_last               4542
_journal_paper_doi               10.1021/acs.joc.9b00245
_journal_volume                  84
_journal_year                    2019
_chemical_formula_moiety         'C20 H19 N O4'
_chemical_formula_sum            'C20 H19 N O4'
_chemical_formula_weight         337.36
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-07-30
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2018-11-12 deposited with the CCDC.
2018-11-12 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 114.7040(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.37710(10)
_cell_length_b                   18.5002(2)
_cell_length_c                   10.29680(10)
_cell_measurement_reflns_used    26130
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      72.0790
_cell_measurement_theta_min      2.4290
_cell_volume                     1622.79(3)
_computing_cell_refinement       'CrystalClear-SM Expert 2.0 r7 (Rigaku, 2011)'
_computing_data_collection       'CrystalClear-SM Expert 2.0 r7 (Rigaku, 2011)'
_computing_data_reduction        'CrystalClear-SM Expert 2.0 r7 (Rigaku, 2011)'
_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_temperature      293(2)
_diffrn_detector                 CCD
_diffrn_detector_area_resol_mean 28.5714
_diffrn_detector_type            'Rigaku Saturn724+'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.997
_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    -92.00 -66.00   0.50    1.00    --  -41.35 -37.00  43.00   52
  2  \w    -34.00  -8.00   0.50    1.00    --  -41.35  37.00-161.00   52
  3  \w     67.00  92.00   0.50    1.00    --   41.35  37.00-161.00   50
  4  \w     20.00  54.00   0.50    1.00    --   41.35 -37.00  43.00   68
  5  \w     99.00 124.00   0.50    4.00    --  101.00  37.00-161.00   50
  6  \w     41.00 100.00   0.50    4.00    --  101.00 -37.00  43.00  118
  7  \w    -47.00 -13.00   0.50    1.00    --    0.00 123.00 169.17   68
  8  \w    -42.00 -17.00   0.50    1.00    --   24.00 151.00 112.89   50
  9  \w    -42.00 -17.00   0.50    1.00    --   24.00 151.00 -80.39   50
 10  \w      3.00  28.00   0.50    1.00    --   32.00  90.00 110.36   50
 11  \w      2.00  27.00   0.50    1.00    --   32.00  91.00 175.27   50
 12  \w      5.00  31.00   0.50    1.00    --   32.00  90.00  34.43   52
 13  \w      4.00  29.00   0.50    1.00    --   32.00  87.00 -14.29   50
 14  \w      2.00  27.00   0.50    1.00    --   32.00  91.00-119.41   50
 15  \w    -90.00 -14.00   0.50    1.00    --  -41.35 138.00 -30.00  152
 16  \w     -5.00  21.00   0.50    1.00    --  -41.35  77.00-150.00   52
 17  \w    -66.00 -32.00   0.50    1.00    --  -41.35  77.00-150.00   68
 18  \w    -95.00 -65.00   0.50    1.00    --  -41.35 138.00 -90.00   60
 19  \w    -57.00 -12.00   0.50    1.00    --  -41.35 138.00 -90.00   90
 20  \w      6.00  60.00   0.50    1.00    --   41.35 -65.00-180.00  108
 21  \w     22.00  96.00   0.50    1.00    --   41.35-138.00 -30.00  148
 22  \w     16.00  42.00   0.50    1.00    --   41.35  77.00  90.00   52
 23  \w      7.00  77.00   0.50    1.00    --   41.35-104.00  60.00  140
 24  \w     16.00  43.00   0.50    1.00    --   41.35  82.00 143.96   54
 25  \w     18.00  43.00   0.50    1.00    --   44.00  82.00 -62.88   50
 26  \w     18.00  43.00   0.50    1.00    --   44.00  82.00 111.75   50
 27  \w     19.00  44.00   0.50    1.00    --   44.00  79.00 171.86   50
 28  \w     19.00  44.00   0.50    1.00    --   44.00  80.00-162.95   50
 29  \w     19.00  44.00   0.50    1.00    --   44.00  79.00 -33.17   50
 30  \w     19.00  44.00   0.50    1.00    --   44.00  79.00-135.43   50
 31  \w     19.00  44.00   0.50    1.00    --   44.00  79.00  37.30   50
 32  \w     18.00  43.00   0.50    1.00    --   44.00  82.00  -5.04   50
 33  \w     19.00  44.00   0.50    1.00    --   44.00  80.00 -89.90   50
 34  \w     27.00  59.00   0.50    1.00    --   52.00  76.00 125.80   64
 35  \w     28.00  75.00   0.50    1.00    --   52.00  77.00-103.24   94
 36  \w     34.00  76.00   0.50    1.00    --   56.00  75.00 -28.80   84
 37  \w     96.00 121.00   0.50    1.00    --   56.00  77.00  86.82   50
 38  \w     34.00  60.00   0.50    1.00    --   56.00  72.00  36.02   52
 39  \w     34.00  60.00   0.50    1.00    --   56.00  77.00  86.82   52
 40  \w     35.00  68.00   0.50    1.00    --   56.00  73.00-132.95   66
 41  \w     74.00 100.00   0.50    1.00    --   56.00  73.00-132.95   52
 42  \w     99.00 125.00   0.50    1.00    --   60.00  77.00 146.67   52
 43  \w     35.00  64.00   0.50    1.00    --   60.00  77.00 146.67   58
 44  \w     40.00  66.00   0.50    1.00    --   60.00  73.00 109.26   52
 45  \w     41.00  85.00   0.50    1.00    --   60.00  63.00 -62.70   88
 46  \w     39.00  70.00   0.50    1.00    --   60.00  66.00 -34.95   62
 47  \w     38.00  91.00   0.50    1.00    --   60.00  70.00   6.11  106
 48  \w     41.00 119.00   0.50    1.00    --   64.00  73.00  63.21  156
 49  \w     39.00  71.00   0.50    1.00    --   64.00  76.00  37.44   64
 50  \w     39.00  71.00   0.50    1.00    --   64.00  77.00-178.46   64
 51  \w     53.00 102.00   0.50    4.00    --   72.00  65.00  37.26   98
 52  \w     52.00 136.00   0.50    4.00    --   72.00  72.00 112.94  168
 53  \w     55.00 119.00   0.50    4.00    --   72.00  58.00 -37.27  128
 54  \w     51.00 140.00   0.50    4.00    --   76.00  76.00-139.66  178
 55  \w    105.00 134.00   0.50    4.00    --   76.00  74.00-104.03   58
 56  \w     53.00  84.00   0.50    4.00    --   76.00  74.00-104.03   62
 57  \w     53.00  87.00   0.50    4.00    --   76.00  73.00  70.71   68
 58  \w     56.00 140.00   0.50    4.00    --   76.00  65.00 161.84  168
 59  \w     55.00 145.00   0.50    4.00    --   80.00  77.00 -23.20  180
 60  \w     56.00  95.00   0.50    4.00    --   80.00  75.00-167.12   78
 61  \w    122.00 153.00   0.50    4.00    --   88.00  76.00  81.65   62
 62  \w     63.00 109.00   0.50    4.00    --   88.00  76.00  81.65   92
 63  \w    123.00 154.00   0.50    4.00    --   96.00  71.00  23.92   62
 64  \w     75.00 112.00   0.50    4.00    --   96.00  71.00  23.92   74
 65  \w     74.00 114.00   0.50    4.00    --  101.00-111.00 120.00   80
 66  \w     77.00 103.00   0.50    4.00    --  101.00-111.00-180.00   52
 67  \w     80.00 137.00   0.50    4.00    --  101.00  68.00-150.00  114
 68  \w    130.00 156.00   0.50    4.00    --  101.00  77.00-150.00   52
 69  \w     41.00 106.00   0.50    4.00    --  101.00 -33.00 -60.00  130
 70  \w     77.00 106.00   0.50    4.00    --  101.00 -33.00-150.00   58
 71  \w     77.00 103.00   0.50    4.00    --  101.00  77.00-150.00   52
 72  \w    104.00 154.00   0.50    4.00    --  101.00  59.00 150.00  100
 73  \w     58.00  84.00   0.50    4.00    --  101.00 -93.00 -30.00   52
 74  \w     74.00 115.00   0.50    4.00    --  101.00-111.00   0.00   82
 75  \w    100.00 153.00   0.50    4.00    --  101.00  33.00  60.00  106
 76  \w     37.00  73.00   0.50    4.00    --  101.00 -68.00  60.00   72
 77  \w     83.00 157.00   0.50    4.00    --  101.00  59.00  90.00  148
 78  \w     35.00  62.00   0.50    4.00    --  101.00-111.00   0.00   54
 79  \w     85.00 150.00   0.50    4.00    --  101.00  59.00 -30.00  130
 80  \w    132.00 157.00   0.50    4.00    --  101.00  77.00 120.00   50
 81  \w     76.00 112.00   0.50    4.00    --  101.00  77.00 120.00   72
 82  \w     83.00 152.00   0.50    4.00    --  101.00  59.00   0.00  138
 83  \w    127.00 157.00   0.50    4.00    --  101.00  77.00 -60.00   60
 84  \w     86.00 112.00   0.50    4.00    --  101.00 -42.00 150.00   52
 85  \w     76.00 102.00   0.50    4.00    --  101.00  77.00  30.00   52
 86  \w     77.00 114.00   0.50    4.00    --  101.00  77.00 -60.00   74
 87  \w     39.00  65.00   0.50    4.00    --  101.00 -42.00 150.00   52
 88  \w     80.00 106.00   0.50    4.00    --  101.00  68.00  30.00   52
 89  \w     83.00 146.00   0.50    4.00    --  101.00  59.00 120.00  126
 90  \w    119.00 145.00   0.50    4.00    --  101.00  77.00-180.00   52
 91  \w    122.00 157.00   0.50    4.00    --  101.00  77.00-120.00   70
 92  \w     39.00  95.00   0.50    4.00    --  101.00 -59.00 -30.00  112
 93  \w    131.00 156.00   0.50    4.00    --  101.00  77.00   0.00   50
 94  \w     76.00 108.00   0.50    4.00    --  101.00  77.00-180.00   64
 95  \w     86.00 154.00   0.50    4.00    --  101.00  59.00-120.00  136
 96  \w     66.00 114.00   0.50    4.00    --  101.00-111.00-150.00   96
 97  \w     76.00 111.00   0.50    4.00    --  101.00  77.00-120.00   70
 98  \w     35.00  60.00   0.50    4.00    --  101.00-111.00-150.00   50
 99  \w     84.00 111.00   0.50    4.00    --  101.00  59.00  60.00   54
100  \w    127.00 157.00   0.50    4.00    --  101.00  59.00  60.00   60
101  \w     77.00 105.00   0.50    4.00    --  101.00  77.00 150.00   56
102  \w     80.00 105.00   0.50    4.00    --  101.00  68.00 -90.00   50
103  \w     77.00 114.00   0.50    4.00    --  101.00  77.00  60.00   74
104  \w    132.00 157.00   0.50    4.00    --  101.00  68.00  30.00   50
105  \w    113.00 154.00   0.50    4.00    --  101.00  93.00  60.00   82
106  \w     83.00 142.00   0.50    4.00    --  101.00  59.00 -90.00  118
107  \w     68.00 115.00   0.50    4.00    --  101.00 -17.00 -60.00   94
108  \w     66.00 126.00   0.50    4.00    --  101.00 -77.00-180.00  120
109  \w     81.00 107.00   0.50    4.00    --  101.00-133.00 -30.00   52
110  \w     87.00 139.00   0.50    4.00    --  101.00  59.00-180.00  104
111  \w     31.00  62.00   0.50    4.00    --  101.00 -17.00 -60.00   62
112  \w     80.00 105.00   0.50    4.00    --  101.00  68.00 -60.00   50
113  \w     85.00 119.00   0.50    4.00    --  101.00 -59.00  30.00   68
114  \w     58.00  89.00   0.50    4.00    --  101.00 -42.00-150.00   62
115  \w     46.00  72.00   0.50    4.00    --  101.00 -59.00  30.00   52
116  \w     83.00 148.00   0.50    4.00    --  101.00  59.00 -60.00  130
117  \w     90.00 121.00   0.50    4.00    --  101.00 -68.00 150.00   62
118  \w     77.00 120.00   0.50    4.00    --  101.00 -68.00  60.00   86
119  \w    125.00 151.00   0.50    4.00    --  101.00  77.00  90.00   52
120  \w     79.00 105.00   0.50    4.00    --  101.00  77.00  90.00   52
121  \w    102.00 127.00   0.50    4.00    --  101.00 -77.00 -30.00   50
122  \w     98.00 129.00   0.50    4.00    --  101.00 -93.00 -30.00   62
123  \w    122.00 156.00   0.50    4.00    --  101.00  77.00 -30.00   68
124  \w     39.00  65.00   0.50    4.00    --  101.00 -33.00-150.00   52
125  \w     37.00  90.00   0.50    4.00    --  101.00 -77.00 -30.00  106
126  \w     76.00 103.00   0.50    4.00    --  101.00  77.00 -30.00   54
127  \w     39.00  64.00   0.50    4.00    --  101.00 -42.00 120.00   50
128  \w     85.00 112.00   0.50    4.00    --  101.00 -42.00 120.00   54
129  \w    128.00 157.00   0.50    4.00    --  101.00  77.00 -90.00   58
130  \w     76.00 116.00   0.50    4.00    --  101.00  77.00 -90.00   80
131  \w     42.00  80.00   0.50    4.00    --  101.00 -68.00 150.00   76
132  \w     76.00 108.00   0.50    4.00    --  101.00  77.00   0.00   64
133  \w     68.00 124.00   0.50    4.00    --  101.00-133.00   0.00  112
;
_diffrn_measurement_device       'AFC12 (Right): Kappa 3 circle'
_diffrn_measurement_device_type  'Rigaku Saturn724+ (2x2 bin mode)'
_diffrn_measurement_method       'profile data from \w-scans'
_diffrn_measurement_specimen_support 'Mitegen 50um'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1749660000
_diffrn_orient_matrix_UB_12      0.0201093000
_diffrn_orient_matrix_UB_13      0.0776324000
_diffrn_orient_matrix_UB_21      0.0306376000
_diffrn_orient_matrix_UB_22      -0.0337429000
_diffrn_orient_matrix_UB_23      -0.1227270000
_diffrn_orient_matrix_UB_31      -0.0338164000
_diffrn_orient_matrix_UB_32      0.0734266000
_diffrn_orient_matrix_UB_33      -0.0777401000
_diffrn_radiation_collimation    0.3
_diffrn_radiation_monochromator  Confocal
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0278
_diffrn_reflns_av_unetI/netI     0.0097
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            33623
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.188
_diffrn_reflns_theta_min         4.781
_diffrn_source                   'Rotating Anode'
_diffrn_source_current           24.0
_diffrn_source_power             1.2
_diffrn_source_target            Mo
_diffrn_source_type              'Rotating Anode'
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    0.789
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.81809
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'CrysAlisPro 1.171.39.35a (Rigaku Oxford Diffraction, 2017) 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    1.381
_exptl_crystal_description       plate
_exptl_crystal_F_000             712
_exptl_crystal_size_max          0.23
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.17
_refine_diff_density_max         0.284
_refine_diff_density_min         -0.256
_refine_diff_density_rms         0.047
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.039
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     227
_refine_ls_number_reflns         3207
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.039
_refine_ls_R_factor_all          0.0333
_refine_ls_R_factor_gt           0.0327
_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^)+(0.0394P)^2^+0.7305P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0827
_refine_ls_wR_factor_ref         0.0831
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3109
_reflns_number_total             3207
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo9b00245_si_006.cif
_cod_data_source_block           428-9285-zra-651_1
_cod_database_code               4034262
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C20 H19 N1 O4'
_shelx_estimated_absorpt_t_max   0.878
_shelx_estimated_absorpt_t_min   0.839
_reflns_odcompleteness_completeness 99.79
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     71.98
_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 Secondary CH2 refined with riding coordinates:
 C00I(H00A,H00B), C00M(H00C,H00D), C00N(H00I,H00M), C00O(H00N,H00O)
2.b Aromatic/amide H refined with riding coordinates:
 C008(H008), C00E(H00E), C00F(H00F), C00G(H00G), C00H(H00H), C00J(H00J),
 C00K(H00K), C00L(H00L)
2.c Idealised Me refined as rotating group:
 C00P(H00P,H00Q,H00R)
;
_shelx_res_checksum              20364
_shelx_hkl_checksum              88006
_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 1.448
_oxdiff_exptl_absorpt_empirical_full_min 0.664