Photoredox-driven tandem ring-opening and vinylation: a route to distal alkenyl ketones from cyclopropenes.
Biswas, Sourabh; Srinivasu, Vinjamuri; Mallick, Manasi; Chandu, Palasetty; Sureshkumar, Devarajulu; Chemical communications (Cambridge, England) 61 (2025) 18388–18391; doi:10.1039/d5cc04546k

data_7135081
_publ_section_title
;
 Photoredox-driven tandem ring-opening and vinylation: a route to distal
 alkenyl ketones from cyclopropenes.
;
_journal_issue                   93
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              18388
_journal_page_last               18391
_journal_paper_doi               10.1039/d5cc04546k
_journal_volume                  61
_journal_year                    2025
_chemical_formula_moiety         '0.069(C32 H34 N4 O9)'
_chemical_formula_sum            'C2.21 H2.34 N0.28 O0.62'
_chemical_formula_weight         42.66
_chemical_name_systematic        'DNP adduct'
_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             2024-05-16
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2024-05-17 deposited with the CCDC.	2025-10-15 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 104.0540(10)
_cell_angle_gamma                90
_cell_formula_units_Z            58
_cell_length_a                   21.4354(2)
_cell_length_b                   9.94870(10)
_cell_length_c                   15.1153(2)
_cell_measurement_reflns_used    24076
_cell_measurement_temperature    281(9)
_cell_measurement_theta_max      68.0590
_cell_measurement_theta_min      2.1230
_cell_volume                     3126.92(6)
_computing_cell_refinement       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      281(9)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix3000
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.995
_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    -48.00  27.00   0.50    0.57    --  -40.58  43.00 144.00  150
  2  \w   -108.00 -24.00   0.50    0.57    --  -40.58 -43.00  -7.00  168
  3  \w    -25.00  48.00   0.50    0.57    --   40.58 -43.00  -7.00  146
  4  \w     24.00 108.00   0.50    0.57    --   40.58  43.00 144.00  168
  5  \w   -150.00 -65.00   0.50    2.26    --  -82.50 -43.00  -7.00  170
  6  \w    -48.00 -15.00   0.50    2.26    --  -82.50  43.00 144.00   66
  7  \w     80.00 164.00   0.50    2.26    --   96.35  43.00 144.00  168
  8  \w   -107.00 -25.00   0.50    0.57    --  -40.58 -38.00   0.00  164
  9  \w   -111.00 -26.00   0.50    0.57    --  -40.58 -25.00  90.00  170
 10  \w   -111.00 -26.00   0.50    0.57    --  -40.58 -25.00 150.00  170
 11  \w    -35.00  24.00   0.50    0.57    --   40.58 -12.00 150.00  118
 12  \w    -35.00  24.00   0.50    0.57    --   40.58 -12.00  90.00  118
 13  \w     41.00 100.00   0.50    0.57    --   40.58-138.00-180.00  118
 14  \w    -35.00  24.00   0.50    0.57    --   40.58 -12.00-150.00  118
 15  \w    -25.00  43.00   0.50    0.57    --   40.58 -38.00-180.00  136
 16  \w    -57.00 -16.00   0.50    2.26    --  -82.50  50.00-120.00   82
 17  \w    -47.00 -15.00   0.50    2.26    --  -82.50  42.00 -30.00   64
 18  \w    -57.00 -16.00   0.50    2.26    --  -82.50  50.00 -60.00   82
 19  \w     30.00  57.00   0.50    2.26    --   96.35 -50.00-180.00   54
 20  \w     75.00 165.00   0.50    2.26    --   96.35  59.00 150.00  180
 21  \w     29.00  83.00   0.50    2.26    --   96.35 -68.00-180.00  108
 22  \w     30.00  57.00   0.50    2.26    --   96.35 -50.00  60.00   54
 23  \w     28.00  68.00   0.50    2.26    --   96.35 -59.00  90.00   80
 24  \w     30.00  57.00   0.50    2.26    --   96.35 -50.00 120.00   54
 25  \w     28.00  68.00   0.50    2.26    --   96.35 -59.00   0.00   80
 26  \w     28.00  68.00   0.50    2.26    --   96.35 -59.00-150.00   80
 27  \w     99.00 160.00   0.50    2.26    --   96.35 117.00  30.00  122
 28  \w     28.00  68.00   0.50    2.26    --   96.35 -59.00 150.00   80
 29  \w    105.00 170.00   0.50    2.26    --   96.35  96.00  30.00  130
 30  \w     30.00  57.00   0.50    2.26    --   96.35 -50.00 -90.00   54
 31  \w     80.00 164.00   0.50    2.26    --   96.35  42.00  90.00  168
 32  \w     81.00 167.00   0.50    2.26    --   96.35  25.00-150.00  172
 33  \w     26.00 127.00   0.50    2.26    --   96.35 -87.00 120.00  202
 34  \w     30.00  57.00   0.50    2.26    --   96.35 -50.00-150.00   54
 35  \w     99.00 160.00   0.50    2.26    --   96.35 117.00  60.00  122
 36  \w     30.00  57.00   0.50    2.26    --   96.35 -50.00  30.00   54
 37  \w     26.00 127.00   0.50    2.26    --   96.35 -87.00 120.00  202
 38  \w    -78.00   4.00   0.50    0.57    --  -40.58 104.00 -60.00  164
 39  \w   -108.00 -17.00   0.50    0.57    --  -40.58 -64.00 -90.00  182
 40  \w   -109.00 -14.00   0.50    0.57    --  -40.58 -77.00-150.00  190
 41  \w   -109.00 -14.00   0.50    0.57    --  -40.58 -77.00 -60.00  190
 42  \w   -109.00 -14.00   0.50    0.57    --  -40.58 -77.00 -30.00  190
 43  \w     14.00 109.00   0.50    0.57    --   40.58  77.00-150.00  190
 44  \w     14.00 109.00   0.50    0.57    --   40.58  77.00  90.00  190
 45  \w     14.00 109.00   0.50    0.57    --   40.58  77.00  30.00  190
 46  \w     18.00  78.00   0.50    0.57    --   40.58-104.00   0.00  120
 47  \w     14.00 109.00   0.50    0.57    --   40.58  77.00 -90.00  190
 48  \w     14.00 109.00   0.50    0.57    --   40.58  77.00 150.00  190
 49  \w     83.00 164.00   0.50    2.26    --   96.35  33.00  30.00  162
 50  \w     80.00 164.00   0.50    2.26    --   96.35  42.00 -30.00  168
 51  \w     44.00 127.00   0.50    2.26    --   96.35-145.00  30.00  166
 52  \w     83.00 164.00   0.50    2.26    --   96.35  33.00 -90.00  162
 53  \w     70.00  95.00   0.50    2.26    --   96.35  77.00 -90.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix3000'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0581655000
_diffrn_orient_matrix_UB_12      -0.0309062000
_diffrn_orient_matrix_UB_13      -0.0398012000
_diffrn_orient_matrix_UB_21      -0.0441570000
_diffrn_orient_matrix_UB_22      -0.0778605000
_diffrn_orient_matrix_UB_23      -0.0790423000
_diffrn_orient_matrix_UB_31      -0.0125989000
_diffrn_orient_matrix_UB_32      0.1302076000
_diffrn_orient_matrix_UB_33      -0.0565970000
_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     0.0161
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            37956
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.117
_diffrn_reflns_theta_min         2.125
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.809
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.83375
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.93a (Rigaku Oxford Diffraction, 2020)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear dark red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.314
_exptl_crystal_description       block
_exptl_crystal_F_000             1304
_exptl_crystal_preparation       'Hexane DCM mixture'
_exptl_crystal_recrystallization_method 'Vapour defusion'
_exptl_crystal_size_max          0.025
_exptl_crystal_size_mid          0.02
_exptl_crystal_size_min          0.015
_refine_diff_density_max         0.737
_refine_diff_density_min         -0.285
_refine_diff_density_rms         0.045
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.092
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     409
_refine_ls_number_reflns         5664
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.092
_refine_ls_R_factor_all          0.0660
_refine_ls_R_factor_gt           0.0580
_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^)+(0.1055P)^2^+0.8148P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1805
_refine_ls_wR_factor_ref         0.1901
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4696
_reflns_number_total             5664
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc04546k2.cif
_cod_data_source_block           sb-al
_cod_depositor_comments          'Adding full bibliography for 7135081.cif.'
_cod_database_code               7135081
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H N O'
_shelx_estimated_absorpt_t_max   0.988
_shelx_estimated_absorpt_t_min   0.980
_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.a Ternary CH refined with riding coordinates:
 C00R(H00R)
2.b Secondary CH2 refined with riding coordinates:
 C00G(H00A,H00B), C00L(H00C,H00D), C00N(H00E,H00F), C00P(H00G,H00H), C00S(H00I,
 H00J)
2.c Aromatic/amide H refined with riding coordinates:
 N003(H003), C00K(H00K), C00M(H00M), C00O(H00O), C00T(H00T), C00Y(H00Y),
 C00Z(H00Z), C010(H010), C011(H011), C012(H012), C013(H013), C015(H015),
 C016(H016), C017(H017)
2.d Idealised Me refined as rotating group:
 C014(H01A,H01B,H01C), C018(H01D,H01E,H01F), C019(H01G,H01H,H01I)
;
_shelx_res_checksum              87437
_shelx_hkl_checksum              15355
_olex2_submission_original_sample_id SB-AL
_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 1.208
_oxdiff_exptl_absorpt_empirical_full_min 0.897