Rhodium-catalyzed isomerization of homoallylic alcohols with a tethered carbonyl group: pathway to 1,6-diketones.
Peng, Shuang; Su, Tong; Yang, Xuan; Li, Jia-Jie; Wan, Jie; Ni, Hai-Liang; Cao, Peng; Hu, Ping; Wang, Bi-Qin; Chen, Bin; Organic & biomolecular chemistry 23 (2025) 5417–5422; doi:10.1039/d5ob00473j

data_7160552
_publ_section_title
;
 Rhodium-catalyzed isomerization of homoallylic alcohols with a tethered
 carbonyl group: pathway to 1,6-diketones.
;
_journal_issue                   22
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              5417
_journal_page_last               5422
_journal_paper_doi               10.1039/d5ob00473j
_journal_volume                  23
_journal_year                    2025
_chemical_formula_moiety         'C20 H22 O2'
_chemical_formula_sum            'C20 H22 O2'
_chemical_formula_weight         294.37
_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     iterative
_audit_creation_date             2024-01-16
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2024-10-14 deposited with the CCDC.	2025-05-09 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 116.075(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   19.3649(4)
_cell_length_b                   5.54250(10)
_cell_length_c                   17.0356(4)
_cell_measurement_reflns_used    10235
_cell_measurement_temperature    295.70(10)
_cell_measurement_theta_max      76.7280
_cell_measurement_theta_min      2.5360
_cell_volume                     1642.33(7)
_computing_cell_refinement       'CrysAlisPro 1.171.41.112a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.112a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.112a (Rigaku OD, 2021)'
_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    'olex2.solve (Bourhis et al., 2015)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      295.70(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.976
_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     40.00  65.00   0.50    0.05    --  106.81 -57.00-150.00   50
  2  \w     97.00 178.00   0.50    0.05    --  106.81  85.00 -46.00  162
  3  \w     94.00 174.00   0.50    0.05    --  106.81  49.00 101.00  160
  4  \w     42.00  91.00   0.50    0.05    --  106.81 -92.00  95.00   98
  5  \w     35.00  68.00   0.50    0.05    --  106.81 -57.00  30.00   66
  6  \w     34.00  65.00   0.50    0.05    --  106.81 -57.00-120.00   62
  7  \w     37.00 107.00   0.50    0.05    --   47.63  49.00 101.00  140
  8  \w    -12.00  25.00   0.50    0.05    --  -47.63  19.00-150.00   74
  9  \w    -64.00 -39.00   0.50    0.05    -- -102.00  57.00-120.00   50
 10  \w    -62.00 -32.00   0.50    0.05    -- -102.00  57.00 -60.00   60
 11  \w   -112.00 -86.00   0.50    0.05    --  -47.63-125.00   0.00   52
 12  \w   -119.00 -89.00   0.50    0.05    --  -47.63-125.00 120.00   60
 13  \w    -39.00  20.00   0.50    0.05    --  -47.63  37.00-150.00  118
 14  \w    -13.00  14.00   0.50    0.05    --  -47.63  19.00-180.00   54
 15  \w    -23.00  63.00   0.50    0.05    --   47.63 -57.00 -30.00  172
 16  \w     66.00  95.00   0.50    0.05    --   47.63-125.00  30.00   58
 17  \w    -64.00 -38.00   0.50    0.05    -- -102.00  57.00 -30.00   52
 18  \w    -60.00 -34.00   0.50    0.05    -- -102.00  57.00 150.00   52
 19  \w   -114.00 -73.00   0.50    0.05    -- -102.00 125.00-150.00   82
 20  \w   -169.00-116.00   0.50    0.05    -- -102.00 -57.00 -60.00  106
 21  \w   -174.00-148.00   0.50    0.05    -- -102.00 -99.00  30.00   52
 22  \w   -130.00 -97.00   0.50    0.05    -- -102.00 -99.00  30.00   66
 23  \w   -134.00-105.00   0.50    0.05    -- -102.00 -37.00-120.00   58
 24  \w    -63.00 -31.00   0.50    0.05    -- -102.00 125.00   0.00   64
 25  \w   -172.00 -83.00   0.50    0.05    -- -102.00 -77.00  90.00  178
 26  \w   -116.00 -90.00   0.50    0.05    -- -102.00 125.00   0.00   52
 27  \w   -175.00-149.00   0.50    0.05    -- -102.00 -37.00-120.00   52
 28  \w    111.00 143.00   0.50    0.05    --  106.81  19.00-180.00   64
 29  \w     48.00 117.00   0.50    0.05    --  106.81-125.00   0.00  138
 30  \w     45.00  77.00   0.50    0.05    --  106.81 -99.00-180.00   64
 31  \w     37.00 105.00   0.50    0.05    --  106.81 -99.00  30.00  136
 32  \w     37.00  63.00   0.50    0.05    --  106.81-125.00  30.00   52
 33  \w     69.00 117.00   0.50    0.05    --  106.81-125.00-180.00   96
 34  \w     44.00  84.00   0.50    0.05    --  106.81 -99.00 -60.00   80
 35  \w     39.00  65.00   0.50    0.05    --  106.81 -57.00-180.00   52
 36  \w     75.00 114.00   0.50    0.05    --  106.81-125.00  30.00   78
 37  \w     35.00  61.00   0.50    0.05    --  106.81-125.00-180.00   52
 38  \w     78.00 107.00   0.50    0.05    --  106.81 -99.00  60.00   58
 39  \w     43.00  71.00   0.50    0.05    --  106.81 -99.00  60.00   56
 40  \w    151.00 178.00   0.50    0.05    --  106.81  19.00-180.00   54
 41  \w     40.00  66.00   0.50    0.05    --  106.81 -57.00 -30.00   52
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0208848000
_diffrn_orient_matrix_UB_12      0.1482100000
_diffrn_orient_matrix_UB_13      0.0630298000
_diffrn_orient_matrix_UB_21      -0.0757726000
_diffrn_orient_matrix_UB_22      0.0784594000
_diffrn_orient_matrix_UB_23      -0.0770735000
_diffrn_orient_matrix_UB_31      -0.0408040000
_diffrn_orient_matrix_UB_32      -0.2217095000
_diffrn_orient_matrix_UB_33      0.0148695000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0313
_diffrn_reflns_av_unetI/netI     0.0209
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.976
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       5
_diffrn_reflns_limit_k_min       -6
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            18261
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.976
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.927
_diffrn_reflns_theta_min         2.540
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.590
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.89815
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.112a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.191
_exptl_crystal_description       block
_exptl_crystal_F_000             632
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.193
_refine_diff_density_min         -0.137
_refine_diff_density_rms         0.027
_refine_ls_extinction_coef       0.0034(10)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2014/7 (Sheldrick 2014'
_refine_ls_goodness_of_fit_ref   1.088
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     200
_refine_ls_number_reflns         3382
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.088
_refine_ls_R_factor_all          0.0512
_refine_ls_R_factor_gt           0.0450
_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^)+(0.0625P)^2^+0.2385P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1271
_refine_ls_wR_factor_ref         0.1322
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2844
_reflns_number_total             3382
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ob00473j2.cif
_cod_data_source_block           exp_5700_auto
_cod_depositor_comments          'Adding full bibliography for 7160552.cif.'
_cod_original_cell_volume        1642.33(6)
_cod_database_code               7160552
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         CHO
_shelx_estimated_absorpt_t_max   0.917
_shelx_estimated_absorpt_t_min   0.891
_diffrn_oxdiff_digest_frames
;
01a829feb2719a5cddbad759afeeb335bd0103474b8
;
_diffrn_oxdiff_digest_hkl
;
01c0d93f1bab28332e1b64f164ba79cf60256a
;
_reflns_odcompleteness_completeness 99.85
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C3(H3A,H3B), C5(H5A,H5B), C6(H6A,H6B), C14(H14A,H14B), C18(H18A,
 H18B)
2.b Aromatic/amide H refined with riding coordinates:
 C9(H9), C10(H10), C11(H11), C12(H12), C13(H13), C15(H15), C16(H16), C17(H17),
 C19(H19), C20(H20)
;
_shelx_res_checksum              34750
_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 1.259
_oxdiff_exptl_absorpt_empirical_full_min 0.802