Thermoneutral synthesis of spiro-1,4-cyclohexadienes by visible-light-driven dearomatization of benzylmalonates
Zhao, Quan-Qing; Rehbein, Julia; Reiser, Oliver; Green Chemistry 24 (2022) 2772–2776; doi:10.1039/D1GC04686A

data_7244371
_publ_section_title
;
 Thermoneutral synthesis of spiro-1,4-cyclohexadienes by
 visible-light-driven dearomatization of benzylmalonates
;
_journal_issue                   7
_journal_name_full               'Green Chemistry'
_journal_page_first              2772
_journal_page_last               2776
_journal_paper_doi               10.1039/D1GC04686A
_journal_volume                  24
_journal_year                    2022
_chemical_formula_moiety         'C26 H32 O4'
_chemical_formula_sum            'C26 H32 O4'
_chemical_formula_weight         408.51
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2021-07-15
_audit_creation_method
;
Olex2 1.3-alpha
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_audit_update_record
;
2021-11-04 deposited with the CCDC.	2022-02-04 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 111.9890(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.56390(10)
_cell_length_b                   21.9239(2)
_cell_length_c                   10.47960(10)
_cell_measurement_reflns_used    23182
_cell_measurement_temperature    123.00(10)
_cell_measurement_theta_max      74.9860
_cell_measurement_theta_min      4.0040
_cell_volume                     2250.54(4)
_computing_cell_refinement       'CrysAlisPro 1.171.41.108a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.108a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.108a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.3-alpha (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-alpha (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      123.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 150'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.993
_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     70.00 104.00   0.50    0.50    --   62.57  10.00  99.00   68
  2  \w    -91.00 -65.00   0.50    0.50    --  -64.16 -10.00 -74.00   52
  3  \w    -91.00 -42.00   0.50    0.50    --  -70.24 -10.00 -74.00   98
  4  \w     80.00 105.00   0.50    2.00    --   75.21  10.00  99.00   50
  5  \w     57.00  82.00   0.50    2.00    --   75.63  10.00  99.00   50
  6  \w     22.00  91.00   0.50    0.50    --   62.57-125.00-180.00  138
  7  \w     72.00 102.00   0.50    0.50    --   62.57  15.00-120.00   60
  8  \w     25.00  67.00   0.50    0.50    --   62.57 -95.00  90.00   84
  9  \w     35.00  68.00   0.50    0.50    --   62.57  15.00-120.00   66
 10  \w     25.00  65.00   0.50    0.50    --   62.57 -95.00  30.00   80
 11  \w     30.00  56.00   0.50    0.50    --   62.57 -95.00 -30.00   52
 12  \w     25.00  60.00   0.50    0.50    --   62.57 -95.00-180.00   70
 13  \w     25.00  50.00   0.50    0.50    --   62.57 -95.00 -90.00   50
 14  \w     31.00  71.00   0.50    0.50    --   62.57 -95.00 -60.00   80
 15  \w    -97.00 -29.00   0.50    0.50    --  -70.24 125.00-180.00  136
 16  \w   -115.00 -52.00   0.50    0.50    --  -70.24 -15.00-120.00  126
 17  \w     74.00 100.00   0.50    2.00    --   75.21-125.00 150.00   52
 18  \w     58.00  84.00   0.50    2.00    --   75.21 -95.00 120.00   52
 19  \w     36.00  61.00   0.50    2.00    --   75.21-125.00 150.00   50
 20  \w     43.00  83.00   0.50    2.00    --   75.21 -95.00-120.00   80
 21  \w   -108.00 -68.00   0.50    2.00    --  -75.50 133.00 -82.67   80
 22  \w   -115.00 -77.00   0.50    2.00    --  -75.50-122.00 -45.60   76
 23  \w   -118.00 -87.00   0.50    2.00    --  -75.50 -37.00 -53.44   62
 24  \w   -108.00 -80.00   0.50    2.00    --  -75.50 -85.00 100.86   56
 25  \w     54.00  80.00   0.50    2.00    --   75.63 -95.00  90.00   52
 26  \w     70.00 104.00   0.50    2.00    --   75.63-125.00  30.00   68
 27  \w     47.00  72.00   0.50    2.00    --   75.63 -95.00 -90.00   50
 28  \w     39.00  64.00   0.50    2.00    --   79.50-127.00 -38.39   50
 29  \w     43.00  69.00   0.50    2.00    --   79.50 -93.00 133.05   52
 30  \w     86.00 112.00   0.50    2.00    --   79.50  22.00 130.42   52
 31  \w     65.00 110.00   0.50    2.00    --   79.50  22.00 170.51   90
 32  \w     86.00 119.00   0.50    2.00    --   79.50  31.00 -17.12   66
 33  \w     66.00 117.00   0.50    2.00    --   79.50  22.00 -38.15  102
 34  \w     54.00 100.00   0.50    2.00    --   79.50-111.00-127.83   92
 35  \w     43.00  83.00   0.50    2.00    --   79.50 -94.00-161.22   80
 36  \w     61.00  96.00   0.50    2.00    --   79.50   6.00 175.51   70
 37  \w     64.00  90.00   0.50    2.00    --   79.50  19.00 131.14   52
 38  \w     52.00  79.00   0.50    2.00    --   79.50-104.00  36.37   54
 39  \w     88.00 114.00   0.50    2.00    --   79.50  17.00-160.64   52
 40  \w     83.00 109.00   0.50    2.00    --   79.50-128.00 121.36   52
 41  \w     60.00 102.00   0.50    2.00    --   79.50-126.00-122.03   84
 42  \w     43.00  76.00   0.50    2.00    --   79.50-128.00 121.36   66
 43  \w     87.00 112.00   0.50    2.00    --   79.50  87.00  85.86   50
 44  \w     68.00 116.00   0.50    2.00    --   79.50  21.00 -88.48   96
 45  \w     64.00 111.00   0.50    2.00    --   79.50-130.00  98.95   94
 46  \w     90.00 122.00   0.50    2.00    --   79.50  53.00 -65.36   64
 47  \w     67.00 119.00   0.50    2.00    --   79.50  22.00  60.14  104
 48  \w     68.00 118.00   0.50    2.00    --   79.50 151.00 -20.42  100
 49  \w     70.00 102.00   0.50    2.00    --   79.50  20.00-121.48   64
 50  \w     73.00 102.00   0.50    2.00    --   79.50 134.00 -42.42   58
 51  \w     40.00 117.00   0.50    2.00    --   79.50-140.00  95.57  154
 52  \w     45.00  99.00   0.50    2.00    --   79.50   6.00-115.88  108
 53  \w     47.00 108.00   0.50    2.00    --   79.50-126.00-155.04  122
 54  \w     77.00 113.00   0.50    2.00    --   79.50   3.00  73.65   72
 55  \w     68.00 115.00   0.50    2.00    --   79.50   4.00 -57.79   94
 56  \w     45.00  70.00   0.50    2.00    --   79.50 -68.00 -87.65   50
 57  \w     73.00 109.00   0.50    2.00    --   79.50-127.00 -38.39   72
 58  \w     40.00  69.00   0.50    2.00    --   79.50 -56.00 -59.36   58
 59  \w     60.00  86.00   0.50    2.00    --   79.50  20.00  42.56   52
 60  \w     60.00  92.00   0.50    2.00    --   79.50-101.00 -39.76   64
 61  \w     49.00 104.00   0.50    2.00    --   79.50-119.00 172.16  110
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix-Arc 150'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1450679000
_diffrn_orient_matrix_UB_12      -0.0091754000
_diffrn_orient_matrix_UB_13      -0.0012679000
_diffrn_orient_matrix_UB_21      0.0581724000
_diffrn_orient_matrix_UB_22      -0.0019497000
_diffrn_orient_matrix_UB_23      0.1584538000
_diffrn_orient_matrix_UB_31      -0.0175702000
_diffrn_orient_matrix_UB_32      0.0696385000
_diffrn_orient_matrix_UB_33      0.0041697000
_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  0.0264
_diffrn_reflns_av_unetI/netI     0.0149
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            45358
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.260
_diffrn_reflns_theta_min         4.033
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.635
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.882
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.108a (Rigaku Oxford Diffraction, 2021)
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    1.206
_exptl_crystal_description       irregular
_exptl_crystal_F_000             880
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.640
_refine_diff_density_min         -0.201
_refine_diff_density_rms         0.044
_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     392
_refine_ls_number_reflns         4621
_refine_ls_number_restraints     30
_refine_ls_restrained_S_all      1.042
_refine_ls_R_factor_all          0.0452
_refine_ls_R_factor_gt           0.0403
_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^)+(0.0526P)^2^+1.0601P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1024
_refine_ls_wR_factor_ref         0.1059
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4122
_reflns_number_total             4621
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1gc04686a2.cif
_cod_data_source_block           u077
_cod_depositor_comments          'Adding full bibliography for 7244371.cif.'
_cod_database_code               7244371
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C26 H32 O4'
_chemical_oxdiff_usercomment     Zhao_Reiser_QQZ-188
_shelx_estimated_absorpt_t_max   0.975
_shelx_estimated_absorpt_t_min   0.939
_reflns_odcompleteness_completeness 98.12
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     75.96
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
C25A \\sim C25 \\sim C26 \\sim C26A: within 1.7A with sigma of 0.005 and sigma
for terminal atoms of 0.005 within 1.7A
3. Others
 Sof(C25A)=Sof(H25C)=Sof(H25D)=Sof(C26A)=Sof(H26D)=Sof(H26E)=Sof(H26F)=1-FVAR(1)
 Sof(C25)=Sof(H25A)=Sof(H25B)=Sof(C26)=Sof(H26A)=Sof(H26B)=Sof(H26C)=FVAR(1)
4.a Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C25(H25A,H25B), C25A(H25C,H25D)
4.b Idealised Me refined as rotating group:
 C26(H26A,H26B,H26C), C26A(H26D,H26E,H26F)
;
_shelx_res_checksum              18066
_olex2_date_sample_data_collection 2021-07-14
_olex2_date_sample_submission    2021-07-13
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems CryoStream 700'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder with inert oil'
_olex2_submission_original_sample_id QQZ-188
_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
- B-factor correction
;
_oxdiff_exptl_absorpt_empirical_full_max 1.761
_oxdiff_exptl_absorpt_empirical_full_min 0.563