Synthesis of 2H-Chromenes via Hydrazine-Catalyzed Ring-Closing Carbonyl-Olefin Metathesis
Zhang, Yunfei; Jermaks, Janis; MacMillan, Samantha N.; Lambert, Tristan H.; ACS Catalysis 9 (2019) 9259–; doi:10.1021/acscatal.9b03656

data_4514622
_publ_section_title
;
 Synthesis of 2H-Chromenes via Hydrazine-Catalyzed Ring-Closing
 Carbonyl-Olefin Metathesis
;
_journal_issue                   10
_journal_name_full               'ACS Catalysis'
_journal_page_first              9259
_journal_paper_doi               10.1021/acscatal.9b03656
_journal_volume                  9
_journal_year                    2019
_chemical_formula_moiety         '2(C2 F3 O2), 2(C19 H27 N2 O), 0.5(C4 H6 N2)'
_chemical_formula_sum            'C44 H57 F6 N5 O6'
_chemical_formula_weight         865.94
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-I 2ya'
_space_group_name_H-M_alt        'I 1 2/a 1'
_symmetry_space_group_name_Hall  '-I 2ya'
_symmetry_space_group_name_H-M   'I 1 2/a 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2019-05-29
_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                 98.4180(5)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   17.95158(9)
_cell_length_b                   10.14969(5)
_cell_length_c                   23.05206(13)
_cell_measurement_reflns_used    63298
_cell_measurement_temperature    99.96(10)
_cell_measurement_theta_max      77.7560
_cell_measurement_theta_min      4.7160
_cell_volume                     4154.90(4)
_computing_cell_refinement       'CrysAlisPro 1.171.40.54a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.54a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.54a (Rigaku OD, 2019)'
_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      99.96(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_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    -36.00  26.00   0.50    0.11    --  -48.30  31.00  44.00  124
  2  \w    -41.00 -13.00   0.50    0.11    --    6.00 126.00  66.38   56
  3  \w    -10.00  15.00   0.50    0.11    --   22.00  99.00  65.59   50
  4  \w      9.00  34.00   0.50    0.11    --   38.00  93.00  69.65   50
  5  \w     27.00  53.00   0.50    0.11    --   50.00  82.00  42.82   52
  6  \w     38.00  63.00   0.50    0.11    --   58.00  74.00  24.38   50
  7  \w     49.00  74.00   0.50    0.11    --   70.00  76.00  20.64   50
  8  \w     43.00  68.00   0.50    0.11    --   62.00  72.00  70.76   50
  9  \w     38.00 122.00   0.50    0.11    --   48.30  31.00  44.00  168
 10  \w     76.00 102.00   0.50    0.11    --   58.00  82.00 129.18   52
 11  \w     71.00 102.00   0.50    0.46    --   90.00  73.00  44.34   62
 12  \w     86.00 139.00   0.50    0.46    --  107.75  77.00  60.00  106
 13  \w    149.00 175.00   0.50    0.46    --  107.75  77.00  90.00   52
 14  \w    148.00 174.00   0.50    0.46    --  107.75  77.00 120.00   52
 15  \w    143.00 177.00   0.50    0.46    --  107.75  44.00 114.26   68
 16  \w    137.00 174.00   0.50    0.46    --  107.75  31.00  44.00   74
 17  \w    151.00 177.00   0.50    0.46    --  107.75  45.00  30.00   52
 18  \w    150.00 175.00   0.50    0.46    --  107.75  77.00 -30.00   50
 19  \w    153.00 178.00   0.50    0.46    --  107.75  61.00 -90.00   50
 20  \w    148.00 174.00   0.50    0.46    --  107.75  77.00-150.00   52
 21  \w    131.00 178.00   0.50    0.46    --  107.75  45.00-180.00   94
 22  \w    126.00 152.00   0.50    0.46    --  107.75  77.00-120.00   52
 23  \w    135.00 172.00   0.50    0.46    --  107.75  77.00 -90.00   74
 24  \w    134.00 162.00   0.50    0.46    --  107.75  70.00  -6.73   56
 25  \w    136.00 173.00   0.50    0.46    --  107.75  45.00 -30.00   74
 26  \w    149.00 178.00   0.50    0.46    --  107.75  15.00 -90.00   58
 27  \w    122.00 173.00   0.50    0.46    --  107.75  45.00 -60.00  102
 28  \w    120.00 172.00   0.50    0.46    --  107.75  77.00   0.00  104
 29  \w    117.00 164.00   0.50    0.46    --  107.75  77.00  30.00   94
 30  \w    122.00 164.00   0.50    0.46    --  107.75 125.00  90.00   84
 31  \w    118.00 148.00   0.50    0.46    --  107.75 125.00  60.00   60
 32  \w     97.00 141.00   0.50    0.46    --  107.75  61.00  90.00   88
 33  \w    129.00 175.00   0.50    0.46    --  107.75  30.00 150.00   92
 34  \w    116.00 154.00   0.50    0.46    --  107.75  30.00  60.00   76
 35  \w    101.00 135.00   0.50    0.46    --  107.75  61.00  30.00   68
 36  \w     98.00 127.00   0.50    0.46    --  107.75  45.00 -30.00   58
 37  \w     98.00 124.00   0.50    0.46    --  107.75  45.00  30.00   52
 38  \w     96.00 162.00   0.50    0.46    --  107.75  61.00  60.00  132
 39  \w    106.00 132.00   0.50    0.46    --  107.75  44.00 114.26   52
 40  \w     89.00 178.00   0.50    0.46    --  107.75  77.00 150.00  178
 41  \w     98.00 151.00   0.50    0.46    --  107.75  15.00 150.00  106
 42  \w     94.00 132.00   0.50    0.46    --  107.75  61.00 120.00   76
 43  \w     90.00 116.00   0.50    0.46    --  107.75  77.00  90.00   52
 44  \w     86.00 112.00   0.50    0.46    --  107.75  77.00  30.00   52
 45  \w     90.00 128.00   0.50    0.46    --  107.75  70.00  -6.73   76
 46  \w     98.00 154.00   0.50    0.46    --  107.75  61.00 -30.00  112
 47  \w    151.00 177.00   0.50    0.46    --  107.75 125.00-120.00   52
 48  \w     94.00 120.00   0.50    0.46    --  107.75  61.00 -90.00   52
 49  \w     93.00 141.00   0.50    0.46    --  107.75  61.00 -60.00   96
 50  \w    104.00 143.00   0.50    0.46    --  107.75  15.00 -90.00   78
 51  \w     86.00 124.00   0.50    0.46    --  107.75  77.00-150.00   76
 52  \w     93.00 131.00   0.50    0.46    --  107.75  61.00-180.00   76
 53  \w     87.00 160.00   0.50    0.46    --  107.75  77.00-180.00  146
 54  \w     92.00 164.00   0.50    0.46    --  107.75 125.00 -90.00  144
 55  \w     94.00 153.00   0.50    0.46    --  107.75  61.00-120.00  118
 56  \w     93.00 157.00   0.50    0.46    --  107.75 125.00-150.00  128
 57  \w     92.00 131.00   0.50    0.46    --  107.75 125.00-120.00   78
 58  \w     89.00 128.00   0.50    0.46    --  107.75  77.00 -90.00   78
 59  \w     86.00 121.00   0.50    0.46    --  107.75  77.00-120.00   70
 60  \w     93.00 144.00   0.50    0.46    --  107.75  61.00-150.00  102
 61  \w     86.00 112.00   0.50    0.46    --  107.75  77.00 -60.00   52
 62  \w     86.00 112.00   0.50    0.46    --  107.75  77.00   0.00   52
 63  \w     86.00 145.00   0.50    0.46    --  107.75  77.00 -30.00  118
 64  \w     71.00  97.00   0.50    0.11    --   54.00  80.00-115.33   52
 65  \w     47.00  73.00   0.50    0.11    --   66.00  71.00 -60.43   52
 66  \w     31.00  63.00   0.50    0.11    --   54.00  80.00-115.33   64
 67  \w     33.00  58.00   0.50    0.11    --   54.00  78.00-165.70   50
 68  \w     48.00  79.00   0.50    0.11    --   70.00  77.00-177.91   62
 69  \w     37.00  62.00   0.50    0.11    --   58.00  75.00 -75.44   50
 70  \w     39.00  65.00   0.50    0.11    --   62.00  80.00 -72.64   52
 71  \w     28.00  56.00   0.50    0.11    --   50.00  80.00 -11.28   56
 72  \w     18.00  43.00   0.50    0.11    --   46.00  91.00-112.14   50
 73  \w    -12.00  29.00   0.50    0.11    --   18.00  98.00 -78.12   82
 74  \w     -2.00  26.00   0.50    0.11    --   30.00  98.00  10.13   56
 75  \w     31.00  57.00   0.50    0.11    --   50.00  77.00  91.67   52
 76  \w     46.00  72.00   0.50    0.11    --   66.00  73.00  92.93   52
 77  \w     30.00  55.00   0.50    0.11    --   54.00  83.00  99.63   50
 78  \w     34.00  65.00   0.50    0.11    --   58.00  82.00 129.18   62
 79  \w     79.00 107.00   0.50    0.46    --  102.00  80.00 145.58   56
 80  \w     93.00 142.00   0.50    0.46    --  107.75  61.00 150.00   98
 81  \w     86.00 122.00   0.50    0.46    --  107.75  77.00 120.00   72
 82  \w     15.00  40.00   0.50    0.11    --   42.00  89.00 159.19   50
 83  \w     40.00  65.00   0.50    0.46    --  107.75 -61.00 -30.00   50
 84  \w     36.00  63.00   0.50    0.46    --  107.75 -61.00   0.00   54
 85  \w     37.00  81.00   0.50    0.46    --  107.75 -77.00 -60.00   88
 86  \w     63.00 106.00   0.50    0.46    --  107.75 -94.00 -60.00   86
 87  \w     75.00 107.00   0.50    0.46    --  107.75-125.00 -30.00   64
 88  \w     81.00 116.00   0.50    0.46    --  107.75-125.00  30.00   70
 89  \w    101.00 131.00   0.50    0.46    --  107.75 -81.00  60.91   60
 90  \w     91.00 116.00   0.50    0.46    --  107.75-125.00  90.00   50
 91  \w     85.00 111.00   0.50    0.46    --  107.75 -89.00 109.83   52
 92  \w     81.00 109.00   0.50    0.46    --  107.75 -94.00 120.00   56
 93  \w     82.00 123.00   0.50    0.46    --  107.75-136.00 112.60   82
 94  \w     73.00  98.00   0.50    0.46    --  107.75 -77.00 150.00   50
 95  \w     61.00 105.00   0.50    0.46    --  107.75 -94.00  90.00   88
 96  \w     76.00 110.00   0.50    0.46    --  107.75-100.00  81.61   68
 97  \w     70.00 114.00   0.50    0.46    --  107.75-125.00  60.00   88
 98  \w     68.00 116.00   0.50    0.46    --  107.75-125.00 -60.00   96
 99  \w     78.00 116.00   0.50    0.46    --  107.75-125.00-150.00   76
100  \w     75.00 100.00   0.50    0.46    --  107.75 -94.00-150.00   50
101  \w     70.00  96.00   0.50    0.46    --  107.75 -77.00-180.00   52
102  \w     42.00  67.00   0.50    0.46    --  107.75 -77.00-180.00   50
103  \w     46.00  71.00   0.50    0.46    --  107.75 -61.00-150.00   50
104  \w     36.00  88.00   0.50    0.46    --  107.75 -77.00 -90.00  104
105  \w     36.00  70.00   0.50    0.46    --  107.75-125.00 -30.00   68
106  \w     37.00  92.00   0.50    0.46    --  107.75 -77.00 -30.00  110
107  \w     36.00  77.00   0.50    0.46    --  107.75 -81.00  60.91   82
108  \w     42.00  68.00   0.50    0.46    --  107.75 -77.00 150.00   52
109  \w     37.00  72.00   0.50    0.46    --  107.75 -89.00 109.83   70
110  \w     41.00  85.00   0.50    0.46    --  107.75-125.00  90.00   88
111  \w     39.00  64.00   0.50    0.46    --  107.75-136.00 112.60   50
112  \w     36.00  61.00   0.50    0.46    --  107.75 -94.00 120.00   50
113  \w     38.00  63.00   0.50    0.46    --  107.75-125.00  60.00   50
114  \w     37.00  63.00   0.50    0.46    --  107.75-100.00  81.61   52
115  \w     36.00  61.00   0.50    0.46    --  107.75 -61.00 120.00   50
116  \w     31.00  95.00   0.50    0.11    --   48.30-125.00  90.00  128
117  \w     37.00  71.00   0.50    0.46    --  107.75 -61.00-120.00   68
118  \w     39.00  64.00   0.50    0.46    --  107.75 -61.00-180.00   50
119  \w     36.00 100.00   0.50    0.46    --  107.75 -94.00-120.00  128
120  \w     42.00  72.00   0.50    0.46    --  107.75-125.00-150.00   60
121  \w     39.00  65.00   0.50    0.46    --  107.75 -94.00-150.00   52
122  \w     36.00  68.00   0.50    0.46    --  107.75 -77.00-120.00   64
123  \w    -25.00  36.00   0.50    0.11    --   48.30 -31.00-115.00  122
124  \w    -52.00 -27.00   0.50    0.11    --  -48.30 -77.00 -60.00   50
125  \w    -66.00 -40.00   0.50    0.11    --  -62.00 -77.00 -47.02   52
126  \w    -76.00 -51.00   0.50    0.46    --  -70.00 -69.00  34.05   50
127  \w    -80.00 -54.00   0.50    0.46    --  -78.00 -82.00  30.80   52
128  \w    -73.00 -47.00   0.50    0.46    --  -70.00 -81.00 105.31   52
129  \w    -74.00 -48.00   0.50    0.46    --  -70.00 -82.00 153.26   52
130  \w    -74.00 -41.00   0.50    0.11    --  -66.00 -83.00 177.02   66
131  \w    -84.00 -57.00   0.50    0.46    --  -78.00 -74.00 133.74   54
132  \w    -92.00 -65.00   0.50    0.46    --  -86.25 -75.00  75.59   54
133  \w    -89.00 -64.00   0.50    0.46    --  -86.25 -77.00  90.00   50
134  \w    -89.00 -62.00   0.50    0.46    --  -86.25 -83.00  56.86   54
135  \w    -92.00 -66.00   0.50    0.46    --  -86.25 -72.00  94.15   52
136  \w    -92.00 -66.00   0.50    0.46    --  -86.25 -77.00 120.00   52
137  \w    -90.00 -63.00   0.50    0.46    --  -86.25 -80.00   9.02   54
138  \w    -84.00 -57.00   0.50    0.46    --  -78.00 -74.00 -33.73   54
139  \w    -81.00 -49.00   0.50    0.46    --  -74.00 -83.00-114.13   64
140  \w    -74.00 -41.00   0.50    0.11    --  -66.00 -83.00-144.04   66
141  \w    -90.00 -64.00   0.50    0.46    --  -82.00 -72.00 -35.53   52
142  \w    -93.00 -66.00   0.50    0.46    --  -86.25 -72.00 -92.05   54
143  \w    -92.00 -62.00   0.50    0.46    --  -86.25 -83.00-121.59   60
144  \w    -92.00 -64.00   0.50    0.46    --  -86.25 -77.00-180.00   56
145  \w   -105.00 -68.00   0.50    0.46    --  -86.25 -67.00-175.86   74
146  \w   -105.00 -65.00   0.50    0.46    --  -86.25 -77.00-150.00   80
147  \w   -121.00 -38.00   0.50    0.11    --  -48.30 -31.00-115.00  166
148  \w    -69.00  20.00   0.50    0.11    --  -48.30  77.00 -60.00  178
149  \w    -47.00 -15.00   0.50    0.46    --  -86.25  45.00-150.00   64
150  \w   -104.00 -58.00   0.50    0.11    --  -48.30 -19.00 -60.00   92
151  \w    -98.00 -65.00   0.50    0.46    --  -86.25 -77.00 -60.00   66
152  \w    -89.00 -63.00   0.50    0.46    --  -86.25 -83.00 -32.04   52
153  \w   -123.00 -98.00   0.50    0.46    --  -86.25 -72.00 -92.05   50
154  \w   -134.00 -83.00   0.50    0.11    --  -66.00 -83.00-144.04  102
155  \w   -135.00 -97.00   0.50    0.46    --  -86.25 -83.00-121.59   76
156  \w   -160.00 -76.00   0.50    0.46    --  -86.25 -31.00-115.00  168
157  \w   -149.00-123.00   0.50    0.46    --  -78.00 -82.00  30.80   52
158  \w   -155.00-129.00   0.50    0.46    --  -86.25 -75.00  75.59   52
159  \w   -120.00 -67.00   0.50    0.46    --  -86.25 -70.00 148.24  106
;
_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      -0.0438855000
_diffrn_orient_matrix_UB_12      0.1160685000
_diffrn_orient_matrix_UB_13      0.0216424000
_diffrn_orient_matrix_UB_21      0.0602783000
_diffrn_orient_matrix_UB_22      0.0964328000
_diffrn_orient_matrix_UB_23      -0.0156812000
_diffrn_orient_matrix_UB_31      -0.0443532000
_diffrn_orient_matrix_UB_32      0.0161094000
_diffrn_orient_matrix_UB_33      -0.0620536000
_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  0.0349
_diffrn_reflns_av_unetI/netI     0.0107
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            82959
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         70.073
_diffrn_reflns_theta_min         4.769
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.931
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.460
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.54a (Rigaku Oxford Diffraction, 2019)
Numerical absorption correction based on gaussian integration over
            a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.384
_exptl_crystal_description       plate
_exptl_crystal_F_000             1832
_exptl_crystal_size_max          0.288
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.064
_refine_diff_density_max         0.293
_refine_diff_density_min         -0.298
_refine_diff_density_rms         0.043
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.039
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     283
_refine_ls_number_reflns         3944
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.040
_refine_ls_R_factor_all          0.0360
_refine_ls_R_factor_gt           0.0354
_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^)+(0.0406P)^2^+4.7194P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0874
_refine_ls_wR_factor_ref         0.0879
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3838
_reflns_number_total             3944
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs9b03656_si_002.cif
_cod_data_source_block           ryz4_abs
_cod_database_code               4514622
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         C22H30F3N2.5O
_chemical_oxdiff_usercomment     'Crystallize from MeCN'
_shelx_estimated_absorpt_t_max   0.943
_shelx_estimated_absorpt_t_min   0.775
_reflns_odcompleteness_completeness 99.93
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     69.95
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 N1-H1
 0.88 with sigma of 0.02
3. Others
 Fixed Sof: H23A(0.5) H23B(0.5) H23C(0.5)
4.a Ternary CH refined with riding coordinates:
 C1(H1A), C4(H4), C6(H6), C14(H14)
4.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C3(H3A,H3B), C5(H5A,H5B), C13(H13A,H13B), C16(H16A,H16B),
 C18(H18A,H18B)
4.c Aromatic/amide H refined with riding coordinates:
 C8(H8), C9(H9), C10(H10), C11(H11)
4.d Idealised Me refined as rotating group:
 C17(H17A,H17B,H17C), C19(H19A,H19B,H19C), C23(H23A,H23B,H23C)
;
_shelx_res_checksum              31818
_shelx_hkl_checksum              58810
_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 1.290
_oxdiff_exptl_absorpt_empirical_full_min 0.802