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_4034264
_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         'C19 H17 N O4'
_chemical_formula_sum            'C19 H17 N O4'
_chemical_formula_weight         323.33
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 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                 90.1840(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.58750(10)
_cell_length_b                   9.82750(10)
_cell_length_c                   16.12470(10)
_cell_measurement_reflns_used    25907
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      71.9380
_cell_measurement_theta_min      2.7850
_cell_volume                     1519.28(2)
_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      100(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 0.999
_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   -102.00 -43.00   0.50    1.00    --  -41.35 -67.00-115.00  118
  2  \w    -35.00  10.00   0.50    1.00    --  -41.35 105.00-100.00   90
  3  \w    -58.00 -18.00   0.50    1.00    --  -41.35  58.00 173.00   80
  4  \w    -88.00 -62.00   0.50    1.00    --  -41.35 -58.00  32.00   52
  5  \w     66.00  91.00   0.50    1.00    --   41.35  67.00  19.00   50
  6  \w    -19.00   6.00   0.50    1.00    --   41.35 -58.00  32.00   50
  7  \w     -4.00  21.00   0.50    1.00    --   41.35 -67.00-115.00   50
  8  \w     -4.00  21.00   0.50    1.00    --   41.35-105.00 158.00   50
  9  \w     40.00  74.00   0.50    1.00    --   41.35-105.00 158.00   68
 10  \w    101.00 148.00   0.50    1.00    --  101.00  67.00  19.00   94
 11  \w     44.00 122.00   0.50    1.00    --  101.00 -67.00-115.00  156
 12  \w     37.00 105.00   0.50    1.00    --  101.00-105.00 158.00  136
 13  \w     82.00 108.00   0.50    1.00    --  101.00 -58.00  32.00   52
 14  \w     96.00 121.00   0.50    1.00    --  101.00  58.00 173.00   50
 15  \w     94.00 119.00   0.50    1.00    --  101.00 105.00-100.00   50
 16  \w    -22.00  59.00   0.50    1.00    --   41.35 -54.00-150.00  162
 17  \w     43.00  68.00   0.50    1.00    --   41.35  58.00 173.00   50
 18  \w    -21.00  27.00   0.50    1.00    --   41.35 -43.00  60.00   96
 19  \w    110.00 156.00   0.50    1.00    --  101.00  33.00 150.00   92
 20  \w     93.00 157.00   0.50    1.00    --  101.00  33.00-180.00  128
 21  \w     93.00 135.00   0.50    1.00    --  101.00  17.00 -30.00   84
 22  \w    108.00 157.00   0.50    1.00    --  101.00  93.00 -60.00   98
 23  \w     81.00 144.00   0.50    1.00    --  101.00 111.00 -30.00  126
 24  \w     38.00 114.00   0.50    1.00    --  101.00 -42.00-120.00  152
 25  \w     81.00 107.00   0.50    1.00    --  101.00  93.00 -90.00   52
 26  \w    112.00 154.00   0.50    1.00    --  101.00  25.00  90.00   84
 27  \w     94.00 119.00   0.50    1.00    --  101.00  67.00  19.00   50
 28  \w    -77.00 -35.00   0.50    1.00    --  -41.35 -54.00-180.00   84
 29  \w     72.00  98.00   0.50    1.00    --   41.35  32.00-180.00   52
 30  \w     53.00  79.00   0.50    1.00    --  101.00 -68.00 -90.00   52
 31  \w     73.00 102.00   0.50    1.00    --  101.00-111.00  90.00   58
 32  \w     68.00 131.00   0.50    1.00    --  101.00 -93.00  90.00  126
 33  \w     90.00 116.00   0.50    1.00    --  101.00 -68.00 -90.00   52
 34  \w     34.00  94.00   0.50    1.00    --  101.00 -17.00-180.00  120
 35  \w     46.00  76.00   0.50    1.00    --  101.00 -59.00 150.00   60
 36  \w     97.00 123.00   0.50    1.00    --  101.00  42.00 -60.00   52
 37  \w     39.00  98.00   0.50    1.00    --  101.00 -25.00 -90.00  118
 38  \w     82.00 125.00   0.50    1.00    --  101.00  68.00  60.00   86
 39  \w     21.00  55.00   0.50    1.00    --   41.35  67.00  18.00   68
 40  \w    -97.00 -71.00   0.50    1.00    --  -41.35 -43.00 120.00   52
 41  \w    -44.00 -10.00   0.50    1.00    --  -41.35  32.00 150.00   68
 42  \w   -103.00 -35.00   0.50    1.00    --  -41.35 -43.00 -60.00  136
 43  \w    -66.00 -38.00   0.50    1.00    --  -41.35 -43.00 120.00   56
 44  \w     30.00  55.00   0.50    1.00    --   41.35 -43.00 -30.00   50
 45  \w      9.00  71.00   0.50    1.00    --   41.35-104.00  30.00  124
 46  \w     -9.00  17.00   0.50    1.00    --   41.35 -77.00-180.00   52
 47  \w     42.00  67.00   0.50    1.00    --   41.35 -77.00-180.00   50
 48  \w    -22.00   4.00   0.50    1.00    --   41.35 -32.00  90.00   52
 49  \w    -20.00  10.00   0.50    1.00    --   41.35 -43.00 -30.00   60
 50  \w     67.00  95.00   0.50    1.00    --   41.35-138.00  30.00   56
 51  \w     83.00 108.00   0.50    1.00    --  101.00  59.00 150.00   50
 52  \w     46.00  74.00   0.50    1.00    --  101.00 -77.00 150.00   56
 53  \w    130.00 156.00   0.50    1.00    --  101.00  59.00 150.00   52
 54  \w     91.00 117.00   0.50    1.00    --  101.00  17.00   0.00   52
 55  \w     48.00 112.00   0.50    1.00    --  101.00 -42.00   0.00  128
 56  \w    105.00 157.00   0.50    1.00    --  101.00  93.00-180.00  104
 57  \w     88.00 114.00   0.50    1.00    --  101.00-111.00  30.00   52
 58  \w     80.00 128.00   0.50    1.00    --  101.00 -87.00 -60.00   96
 59  \w     38.00  86.00   0.50    1.00    --  101.00 -68.00   0.00   96
 60  \w     77.00 103.00   0.50    1.00    --  101.00 -68.00-150.00   52
 61  \w     80.00 111.00   0.50    1.00    --  101.00-111.00 -60.00   62
 62  \w    102.00 143.00   0.50    1.00    --  101.00  25.00 150.00   82
 63  \w     35.00  75.00   0.50    1.00    --  101.00-111.00 -60.00   80
 64  \w     61.00  87.00   0.50    1.00    --  101.00-111.00-180.00   52
 65  \w    132.00 157.00   0.50    1.00    --  101.00  17.00   0.00   50
 66  \w    131.00 157.00   0.50    1.00    --  101.00  33.00 -90.00   52
 67  \w     64.00 109.00   0.50    1.00    --  101.00 -33.00 120.00   90
 68  \w    117.00 143.00   0.50    1.00    --  101.00  68.00  30.00   52
 69  \w     39.00  64.00   0.50    1.00    --  101.00-111.00 150.00   50
 70  \w    113.00 139.00   0.50    1.00    --  101.00  25.00 120.00   52
 71  \w    115.00 141.00   0.50    1.00    --  101.00  33.00-120.00   52
 72  \w     59.00 119.00   0.50    1.00    --  101.00-133.00 -90.00  120
 73  \w     81.00 123.00   0.50    1.00    --  101.00 -77.00 150.00   84
 74  \w     75.00 108.00   0.50    1.00    --  101.00 -50.00 150.00   66
 75  \w     47.00  73.00   0.50    1.00    --  101.00-111.00-150.00   52
 76  \w     84.00 111.00   0.50    1.00    --  101.00-111.00 -30.00   54
 77  \w     80.00 117.00   0.50    1.00    --  101.00-116.00 -68.73   74
 78  \w     75.00 110.00   0.50    1.00    --  101.00 -25.00   0.00   70
 79  \w     98.00 124.00   0.50    1.00    --  101.00-133.00-180.00   52
 80  \w     54.00 110.00   0.50    1.00    --  101.00 -59.00   0.00  112
 81  \w     21.00  47.00   0.50    1.00    --   41.35  77.00-180.00   52
 82  \w    -39.00 -14.00   0.50    1.00    --    8.00 123.00 -58.56   50
 83  \w    -22.00   3.00   0.50    1.00    --   20.00 115.00 142.19   50
 84  \w    -10.00  15.00   0.50    1.00    --   24.00 101.00 114.61   50
 85  \w     -3.00  22.00   0.50    1.00    --   28.00  94.00-129.43   50
 86  \w     -3.00  22.00   0.50    1.00    --   28.00  95.00  -4.30   50
 87  \w      2.00  27.00   0.50    1.00    --   32.00  91.00  89.78   50
 88  \w      5.00  30.00   0.50    1.00    --   32.00  86.00  30.51   50
 89  \w      2.00  27.00   0.50    1.00    --   32.00  91.00 -70.51   50
 90  \w     11.00  36.00   0.50    1.00    --   36.00  81.00 165.37   50
 91  \w      9.00  34.00   0.50    1.00    --   36.00  85.00  76.32   50
 92  \w     16.00  41.00   0.50    1.00    --   41.35  81.00 -30.40   50
 93  \w     18.00  43.00   0.50    1.00    --   44.00  82.00  23.87   50
 94  \w     19.00  44.00   0.50    1.00    --   44.00  81.00-114.55   50
 95  \w     19.00  44.00   0.50    1.00    --   44.00  81.00  78.01   50
 96  \w     19.00  44.00   0.50    1.00    --   44.00  79.00 -75.27   50
 97  \w     19.00  44.00   0.50    1.00    --   44.00  81.00 -18.59   50
 98  \w     18.00  43.00   0.50    1.00    --   44.00  82.00 128.14   50
 99  \w     27.00  52.00   0.50    1.00    --   52.00  77.00-159.07   50
100  \w     31.00  57.00   0.50    1.00    --   52.00  75.00 -35.06   52
101  \w     31.00  57.00   0.50    1.00    --   52.00  76.00  43.24   52
102  \w     31.00  57.00   0.50    1.00    --   56.00  76.00 103.45   52
103  \w     37.00  63.00   0.50    1.00    --   56.00  76.00 -74.40   52
104  \w     37.00  63.00   0.50    1.00    --   56.00  75.00   9.82   52
105  \w     37.00  63.00   0.50    1.00    --   60.00  76.00  55.93   52
106  \w     37.00  65.00   0.50    1.00    --   60.00  77.00-116.10   56
107  \w     35.00  60.00   0.50    1.00    --   60.00  77.00 -13.54   50
108  \w     40.00  65.00   0.50    1.00    --   64.00  75.00 127.08   50
109  \w     45.00  71.00   0.50    1.00    --   64.00  69.00-136.17   52
110  \w     42.00  69.00   0.50    1.00    --   64.00  76.00 154.17   54
111  \w    104.00 129.00   0.50    1.00    --   64.00  76.00 154.17   50
112  \w     55.00  81.00   0.50    1.00    --   64.00  67.00-111.06   52
113  \w     43.00  74.00   0.50    1.00    --   64.00  70.00  88.33   62
114  \w     41.00  67.00   0.50    1.00    --   64.00  73.00 -39.43   52
115  \w     43.00  68.00   0.50    1.00    --   68.00  76.00 105.82   50
116  \w    107.00 132.00   0.50    1.00    --   68.00  67.00  -9.46   50
117  \w     58.00  90.00   0.50    1.00    --   68.00  67.00  -9.46   64
118  \w     97.00 123.00   0.50    1.00    --   68.00  76.00 105.82   52
119  \w     50.00 103.00   0.50    1.00    --   72.00  69.00  44.33  106
120  \w     48.00  76.00   0.50    1.00    --   72.00  75.00 136.12   56
121  \w     59.00  85.00   0.50    1.00    --   76.00  64.00-132.59   52
122  \w    114.00 139.00   0.50    1.00    --   76.00  69.00 -79.36   50
123  \w     54.00  79.00   0.50    1.00    --   76.00  69.00 -79.36   50
124  \w     57.00  83.00   0.50    1.00    --   76.00  71.00 138.00   52
125  \w     53.00  78.00   0.50    1.00    --   76.00  74.00   6.73   50
126  \w     56.00  82.00   0.50    1.00    --   80.00  75.00 174.75   52
127  \w    106.00 145.00   0.50    1.00    --   84.00  74.00 -43.08   78
128  \w     61.00  86.00   0.50    1.00    --   84.00  74.00 -43.08   50
129  \w     60.00  97.00   0.50    1.00    --   84.00  75.00  91.57   74
130  \w     69.00  95.00   0.50    1.00    --   88.00  61.00  77.98   52
131  \w     74.00 100.00   0.50    1.00    --   92.00  69.00-122.61   52
132  \w     75.00 101.00   0.50    1.00    --   96.00  66.00-141.78   52
133  \w     76.00 118.00   0.50    1.00    --  101.00  77.00-120.00   84
134  \w    111.00 137.00   0.50    1.00    --  101.00  77.00-150.00   52
135  \w    107.00 153.00   0.50    1.00    --  101.00  77.00 -30.00   92
136  \w     87.00 113.00   0.50    1.00    --  101.00  59.00 120.00   52
137  \w     76.00 109.00   0.50    1.00    --  101.00  77.00-150.00   66
138  \w     78.00 112.00   0.50    1.00    --  101.00  77.00  30.00   68
139  \w     77.00 102.00   0.50    1.00    --  101.00  77.00 -30.00   50
140  \w    124.00 150.00   0.50    1.00    --  101.00  77.00 120.00   52
141  \w     80.00 135.00   0.50    1.00    --  101.00  77.00  60.00  110
142  \w     76.00 101.00   0.50    1.00    --  101.00  77.00 120.00   50
143  \w     84.00 109.00   0.50    1.00    --  101.00 -33.00 -30.00   50
144  \w     26.00  94.00   0.50    1.00    --  101.00  -8.00 -30.00  136
145  \w    132.00 157.00   0.50    1.00    --  101.00  68.00  90.00   50
146  \w     46.00  72.00   0.50    1.00    --  101.00 -33.00 -30.00   52
147  \w     80.00 112.00   0.50    1.00    --  101.00  68.00 -30.00   64
148  \w     80.00 106.00   0.50    1.00    --  101.00  68.00-120.00   52
149  \w    122.00 156.00   0.50    1.00    --  101.00  77.00   0.00   68
150  \w    127.00 152.00   0.50    1.00    --  101.00  77.00 -90.00   50
151  \w     76.00 102.00   0.50    1.00    --  101.00  77.00 -90.00   52
152  \w     77.00 103.00   0.50    1.00    --  101.00  77.00   0.00   52
153  \w    124.00 150.00   0.50    1.00    --  101.00  77.00 150.00   52
154  \w     80.00 106.00   0.50    1.00    --  101.00  68.00  30.00   52
155  \w     80.00 107.00   0.50    1.00    --  101.00  68.00 -90.00   54
156  \w     76.00 110.00   0.50    1.00    --  101.00  77.00 150.00   68
157  \w    132.00 157.00   0.50    1.00    --  101.00  77.00  90.00   50
158  \w     41.00  67.00   0.50    1.00    --  101.00 -25.00  60.00   52
159  \w     82.00 109.00   0.50    1.00    --  101.00 -25.00  60.00   54
160  \w     83.00 109.00   0.50    1.00    --  101.00  59.00  60.00   52
161  \w     85.00 111.00   0.50    1.00    --  101.00  59.00  30.00   52
162  \w     86.00 114.00   0.50    1.00    --  101.00  59.00   0.00   56
163  \w     77.00 103.00   0.50    1.00    --  101.00  77.00  90.00   52
164  \w    114.00 140.00   0.50    1.00    --  101.00  77.00 -60.00   52
165  \w    121.00 155.00   0.50    1.00    --  101.00  68.00-120.00   68
166  \w     80.00 106.00   0.50    1.00    --  101.00  77.00 -60.00   52
167  \w     80.00 115.00   0.50    1.00    --  101.00  68.00  90.00   70
168  \w     76.00 129.00   0.50    1.00    --  101.00  77.00-180.00  106
169  \w    115.00 142.00   0.50    1.00    --  101.00 111.00  60.00   54
170  \w    119.00 153.00   0.50    1.00    --  101.00 111.00 -90.00   68
;
_diffrn_measurement_device       'AFC12 (Right): Kappa 3 circle'
_diffrn_measurement_device_type
'SuperNova, Single source at offset/far, HyPix3000'
_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      -0.1357044000
_diffrn_orient_matrix_UB_12      0.0245555000
_diffrn_orient_matrix_UB_13      -0.0491967000
_diffrn_orient_matrix_UB_21      -0.0756527000
_diffrn_orient_matrix_UB_22      -0.1054994000
_diffrn_orient_matrix_UB_23      0.0543617000
_diffrn_orient_matrix_UB_31      -0.0410250000
_diffrn_orient_matrix_UB_32      0.1133740000
_diffrn_orient_matrix_UB_33      0.0612123000
_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  0.0242
_diffrn_reflns_av_unetI/netI     0.0087
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            33745
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.018
_diffrn_reflns_theta_min         4.612
_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    0.818
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.79020
_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 whiteish colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   whiteish
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.414
_exptl_crystal_description       needle
_exptl_crystal_F_000             680
_exptl_crystal_size_max          0.21
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.269
_refine_diff_density_min         -0.258
_refine_diff_density_rms         0.046
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.059
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     217
_refine_ls_number_reflns         2979
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.059
_refine_ls_R_factor_all          0.0336
_refine_ls_R_factor_gt           0.0330
_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^)+(0.0402P)^2^+0.7021P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0820
_refine_ls_wR_factor_ref         0.0825
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2911
_reflns_number_total             2979
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo9b00245_si_004.cif
_cod_data_source_block           1ver0-428-8797_zra-567
_cod_database_code               4034264
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C19 H17 N O4'
_shelx_estimated_absorpt_t_max   0.853
_shelx_estimated_absorpt_t_min   0.847
_reflns_odcompleteness_completeness 99.65
_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
2.a Secondary CH2 refined with riding coordinates:
 C00H(H00B,H00C), C00I(H00D,H00H), C00J(H00I,H00J), C00L(H00L,H00M)
2.b Aromatic/amide H refined with riding coordinates:
 C006(H006), C00A(H00A), C00E(H00E), C00F(H00F), C00G(H00G), C00K(H00K),
 C00M(H00N), C00N(H00O), C00O(H00P)
;
_shelx_res_checksum              73085
_shelx_hkl_checksum              38653
_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 1.699
_oxdiff_exptl_absorpt_empirical_full_min 0.721