Efficient Piancatelli rearrangement of HMF derivatives under microwave activation or subcritical water conditions to produce functionalized hydroxylated cyclopentenones.
Youssef-Saliba, Sparta; Mayet, Clémentine; Elslande, Elsa Van; Le Goff, Géraldine; Betzer, Jean-François; Organic & biomolecular chemistry 23 (2025) 2683–2690; doi:10.1039/d4ob01899k

data_7160362
_publ_section_title
;
 Efficient Piancatelli rearrangement of HMF derivatives under microwave
 activation or subcritical water conditions to produce functionalized
 hydroxylated cyclopentenones.
;
_journal_issue                   11
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              2683
_journal_page_last               2690
_journal_paper_doi               10.1039/d4ob01899k
_journal_volume                  23
_journal_year                    2025
_chemical_formula_moiety         'C35 H48 N2 O8 Rh2'
_chemical_formula_sum            'C35 H48 N2 O8 Rh2'
_chemical_formula_weight         830.57
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_block_doi                 10.5517/ccdc.csd.cc2l01pc
_audit_creation_date             2024-09-11
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2024-09-11 deposited with the CCDC.	2025-02-05 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 95.754(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.6750(4)
_cell_length_b                   16.8487(5)
_cell_length_c                   21.2526(7)
_cell_measurement_reflns_used    18067
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      30.9910
_cell_measurement_theta_min      2.5430
_cell_volume                     3803.2(2)
_computing_cell_refinement       'CrysAlisPro 1.171.43.134a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.134a 64-bit (release 09-08-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.43.134a (Rigaku OD, 2024)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'Dectris PILATUS3 R 200K-A area detector'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_detector_type            'Hybrid Photon Counting area detector'
_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 -85.00 -8.00 0.50 20.00 -- -0.60 -76.00 -94.00 154
 2 \w -50.00 33.00 0.50 20.00 -- -0.60 -82.00-180.00 166
 3 \w 17.00 43.00 0.50 20.00 -- -0.60 19.00 120.00 52
 4 \w 49.00 89.00 0.50 20.00 -- -0.60 19.00 120.00 80
 5 \w -29.00 -2.00 0.50 20.00 -- -0.60 -77.00 30.00 54
 6 \w -75.00 29.00 0.50 20.00 -- -0.60 -77.00 90.00 208
 7 \w -7.00 21.00 0.50 20.00 -- -0.60 -57.00 30.00 56
 8 \w -55.00 -12.00 0.50 20.00 -- -0.60 -77.00-150.00 86
;
_diffrn_measurement_device       'kappa gonio four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB PRO'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0004850000
_diffrn_orient_matrix_UB_12      -0.0308116000
_diffrn_orient_matrix_UB_13      0.0226864000
_diffrn_orient_matrix_UB_21      0.0521321000
_diffrn_orient_matrix_UB_22      0.0177540000
_diffrn_orient_matrix_UB_23      0.0180385000
_diffrn_orient_matrix_UB_31      -0.0417792000
_diffrn_orient_matrix_UB_32      0.0225084000
_diffrn_orient_matrix_UB_33      0.0168743000
_diffrn_radiation_collimation    '0.3 mm'
_diffrn_radiation_monochromator
'Rigaku Integrated Confocal MaxFlux double bounce multi-layer mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0388
_diffrn_reflns_av_unetI/netI     0.0219
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            55660
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.372
_diffrn_reflns_theta_min         2.267
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'Rigaku micromax 003'
_exptl_absorpt_coefficient_mu    0.916
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.39300
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.134a (Rigaku Oxford Diffraction, 2024)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            purple
_exptl_crystal_colour_primary    purple
_exptl_crystal_density_diffrn    1.451
_exptl_crystal_description       'rect. Prism'
_exptl_crystal_F_000             1704
_exptl_crystal_preparation       'slow evaporation'
_exptl_crystal_size_max          0.46
_exptl_crystal_size_mid          0.19
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.550
_refine_diff_density_min         -0.594
_refine_diff_density_rms         0.052
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.072
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     440
_refine_ls_number_reflns         7771
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.072
_refine_ls_R_factor_all          0.0314
_refine_ls_R_factor_gt           0.0252
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0220P)^2^+2.5621P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0588
_refine_ls_wR_factor_ref         0.0624
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6884
_reflns_number_total             7771
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4ob01899k2.cif
_cod_data_source_block           SYS195F0
_cod_depositor_comments          'Adding full bibliography for 7160362.cif.'
_cod_database_code               7160362
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C35H48N2O8Rh2
_shelx_estimated_absorpt_t_max   0.914
_shelx_estimated_absorpt_t_min   0.678
_reflns_odcompleteness_completeness 99.81
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C21(H21), C33(H33), C30(H30)
2.b Aromatic/amide H refined with riding coordinates:
 C15(H15), C16(H16), C10(H10), C17(H17), C11(H11), C28(H28), C27(H27), C29(H29)
2.c Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C4(H4A,H4B,H4C), C6(H6A,H6B,H6C), C20(H20A,H20B,H20C),
 C2(H2A,H2B,H2C), C34(H34A,H34B,H34C), C23(H23A,H23B,H23C), C22(H22A,H22B,H22C),
  C19(H19A,H19B,H19C), C32(H32A,H32B,H32C), C35(H35A,H35B,H35C), C31(H31A,H31B,
 H31C)
;
_shelx_res_checksum              77786
_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 2.562
_oxdiff_exptl_absorpt_empirical_full_min 0.465