Electrochemically driven green synthesis to unlock sustainable routes to β-keto spirolactones
MacLean, Ian; García, Montaña J.; Cabrera, Silvia; Marzo, Leyre; Alemán, José; Green Chemistry 26 (2024) 6553–6558; doi:10.1039/D4GC01127A

data_7248494
_publ_section_title
;
 Electrochemically driven green synthesis to unlock sustainable routes to
 \b-keto spirolactones
;
_journal_issue                   11
_journal_name_full               'Green Chemistry'
_journal_page_first              6553
_journal_page_last               6558
_journal_paper_doi               10.1039/D4GC01127A
_journal_volume                  26
_journal_year                    2024
_chemical_formula_moiety         'C28 H27 N O2, 3.6(O)'
_chemical_formula_sum            'C28 H27 N O5.6'
_chemical_formula_weight         467.10
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-09-20
_audit_creation_method
;
Olex2 1.5-ac5-024
(compiled 2022.04.12 svn.rca3783a0 for Rigaku Oxford Diffraction, GUI svn.r6498)
;
_audit_update_record
;
2024-03-04 deposited with the CCDC.	2024-04-18 downloaded from the CCDC.
;
_cell_angle_alpha                93.410(2)
_cell_angle_beta                 99.781(2)
_cell_angle_gamma                103.653(2)
_cell_formula_units_Z            2
_cell_length_a                   8.90130(10)
_cell_length_b                   10.1017(2)
_cell_length_c                   15.3407(3)
_cell_measurement_reflns_used    11050
_cell_measurement_temperature    250.00(10)
_cell_measurement_theta_max      68.0780
_cell_measurement_theta_min      2.9620
_cell_volume                     1313.79(4)
_computing_cell_refinement       'CrysAlisPro 1.171.42.101a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.101a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.101a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5-ac5-024 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-ac5-024 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      250.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 100'
_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     30.00 112.00   0.50    0.20    --  106.21-125.00-150.00  164
  2  \w     30.00 112.00   0.50    0.20    --  106.21-125.00 -60.00  164
  3  \w     30.00 112.00   0.50    0.20    --  106.21-125.00 -30.00  164
  4  \w      5.00  94.00   0.50    0.10    --   45.89-107.00 101.00  178
  5  \w     31.00 107.00   0.50    0.20    --  106.21-107.00 101.00  152
  6  \w     33.00 105.00   0.50    0.20    --  106.21 -95.00-120.00  144
  7  \w     36.00 109.00   0.50    0.20    --  106.21 -77.00 -90.00  146
  8  \w     25.00  54.00   0.50    0.20    --  106.21 -45.00 -30.00   58
  9  \w     29.00  75.00   0.50    0.20    --  106.21 -61.00  30.00   92
 10  \w     29.00  75.00   0.50    0.20    --  106.21 -61.00  90.00   92
 11  \w     29.00  75.00   0.50    0.20    --  106.21 -61.00 120.00   92
 12  \w     25.00  54.00   0.50    0.20    --  106.21 -45.00  60.00   58
 13  \w    -37.00  30.00   0.50    0.10    --   45.89 -19.00 -30.00  134
 14  \w     81.00 178.00   0.50    0.20    --  106.21  61.00-150.00  194
 15  \w     32.00 133.00   0.50    0.10    --   62.00  76.00 114.40  202
 16  \w     13.00  42.00   0.50    0.10    --   45.89  80.00  -4.23   58
 17  \w     32.00 133.00   0.50    0.10    --   62.00  76.00 -40.39  202
 18  \w     32.00 133.00   0.50    0.10    --   62.00  76.00-179.04  202
 19  \w     16.00  42.00   0.50    0.10    --   50.00  83.00-126.20   52
 20  \w     12.00  42.00   0.50    0.10    --   50.00  89.00 -75.48   60
 21  \w     16.00  42.00   0.50    0.10    --   54.00  89.00 141.37   52
 22  \w     12.00  42.00   0.50    0.10    --   50.00  89.00  72.84   60
 23  \w     90.00 178.00   0.50    0.20    --  106.21 107.00-160.00  176
 24  \w    -95.00   1.00   0.50    0.10    --  -47.39 107.00-160.00  192
 25  \w   -107.00 -13.00   0.50    0.20    --  -88.28 107.00-160.00  188
 26  \w   -120.00 -19.00   0.50    0.20    --  -95.50 136.00 -56.46  202
 27  \w   -124.00 -22.00   0.50    0.20    --  -95.50 142.00 -37.30  204
 28  \w   -108.00 -20.00   0.50    0.20    --  -95.50 111.00 148.77  176
 29  \w   -102.00 -18.00   0.50    0.20    --  -88.28  77.00 120.00  168
 30  \w    -32.00  -6.00   0.50    0.20    --  -88.28  30.00 150.00   52
 31  \w    -32.00  -6.00   0.50    0.20    --  -88.28  30.00  90.00   52
 32  \w    -32.00  -6.00   0.50    0.20    --  -88.28  30.00  60.00   52
 33  \w    -32.00  -6.00   0.50    0.20    --  -88.28  30.00  30.00   52
 34  \w    -23.00  35.00   0.50    0.10    --  -47.39  19.00 -30.00  116
 35  \w    -32.00  -6.00   0.50    0.20    --  -88.28  30.00-180.00   52
 36  \w   -163.00 -83.00   0.50    0.20    --  -88.28-107.00 101.00  160
 37  \w   -164.00 -74.00   0.50    0.20    --  -88.28-125.00 150.00  180
 38  \w   -171.00 -70.00   0.50    0.20    --  -95.50 -64.00 165.85  202
 39  \w   -147.00 -45.00   0.50    0.10    --  -70.00 -60.00  40.58  204
 40  \w   -166.00 -64.00   0.50    0.20    --  -95.50 -77.00  -7.61  204
 41  \w   -168.00 -67.00   0.50    0.20    --  -95.50 -72.00 -36.08  202
 42  \w   -159.00-113.00   0.50    0.20    --  -88.28 -77.00 -90.00   92
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, HyPix-Arc 100'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0614784000
_diffrn_orient_matrix_UB_12      -0.0171976000
_diffrn_orient_matrix_UB_13      -0.0869300000
_diffrn_orient_matrix_UB_21      0.1231201000
_diffrn_orient_matrix_UB_22      -0.0686243000
_diffrn_orient_matrix_UB_23      0.0482360000
_diffrn_orient_matrix_UB_31      -0.1181767000
_diffrn_orient_matrix_UB_32      -0.1410480000
_diffrn_orient_matrix_UB_33      -0.0247901000
_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  0.0279
_diffrn_reflns_av_unetI/netI     0.0196
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            24018
_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         68.437
_diffrn_reflns_theta_min         2.939
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'PhotonJet R (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.671
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.676
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.101a (Rigaku Oxford Diffraction, 2023)
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            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.181
_exptl_crystal_description       plate
_exptl_crystal_F_000             494
_exptl_crystal_recrystallization_method 'obtained from dichloromethane'
_exptl_crystal_size_max          0.302
_exptl_crystal_size_mid          0.136
_exptl_crystal_size_min          0.021
_refine_diff_density_max         0.696
_refine_diff_density_min         -0.321
_refine_diff_density_rms         0.073
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.097
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     329
_refine_ls_number_reflns         4817
_refine_ls_number_restraints     278
_refine_ls_restrained_S_all      1.087
_refine_ls_R_factor_all          0.0827
_refine_ls_R_factor_gt           0.0766
_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^)+(0.1486P)^2^+0.4142P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2364
_refine_ls_wR_factor_ref         0.2430
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4132
_reflns_number_total             4817
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4gc01127a2.cif
_cod_data_source_block           03904
_cod_depositor_comments          'Adding full bibliography for 7248494.cif.'
_cod_original_formula_sum        'C28 H27 N O5.60'
_cod_database_code               7248494
_shelx_shelxl_version_number     2019/1
_chemical_oxdiff_formula         C28H27NO2
_chemical_oxdiff_usercomment     IMG-150.F4
_shelx_estimated_absorpt_t_max   0.986
_shelx_estimated_absorpt_t_min   0.823
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C26-C27A = C27A-C28A = C26-C27B = C27B-C28B
 1.5 with sigma of 0.02
 C25-C27A = C25-C27B = C26-C28A = C26-C28B
 2.5 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
Uanis(C27A) = Uanis(C27B)
Uanis(C28A) = Uanis(C28B)
4. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(H26C)=Sof(H26D)=Sof(C27B)=Sof(H27C)=Sof(H27D)=Sof(C28B)=Sof(H28D)=
 Sof(H28E)=Sof(H28F)=1-FVAR(1)
 Sof(H26A)=Sof(H26B)=Sof(C27A)=Sof(H27A)=Sof(H27B)=Sof(C28A)=Sof(H28A)=
 Sof(H28B)=Sof(H28C)=FVAR(1)
 Fixed Sof: O3W(0.25) O4W(0.5) O5W(0.75) O6W(0.3) O7W(0.25) O8W(0.3) O9W(0.5)
 O10W(0.25) O11W(0.25) O12W(0.25)
6.a Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C12(H12A,H12B), C25(H25A,H25B), C26(H26A,H26B), C26(H26C,H26D),
 C27A(H27A,H27B), C27B(H27C,H27D)
6.b Aromatic/amide H refined with riding coordinates:
 C7(H7), C8(H8), C9(H9), C10(H10), C14(H14), C15(H15), C16(H16), C17(H17),
 C18(H18), C20(H20), C21(H21), C22(H22), C23(H23), C24(H24)
6.c Idealised Me refined as rotating group:
 C28A(H28A,H28B,H28C), C28B(H28D,H28E,H28F)
;
_shelx_res_checksum              91836
_shelx_hkl_checksum              71360
_olex2_exptl_crystal_mounting_method 'placed on a MiTeGen micromount'
_olex2_submission_original_sample_id IMG-150.F4
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.650
_oxdiff_exptl_absorpt_empirical_full_min 0.767