Meyer-Schuster rearrangement/allylic alkenylation of propynolaldehydes with olefins to synthesize skipped 1,4-dienes.
Shen, Cheng-Ping; Zhu, Hai-Tao; Li, Guo-Hua; Chang, Xin; Xi, Jia-Jun; Zhou, Ni-Ni; Zhou, An-Xi; Organic & biomolecular chemistry 23 (2025) 3870–3874; doi:10.1039/d5ob00173k

data_7160408
_publ_section_title
;
 Meyer-Schuster rearrangement/allylic alkenylation of propynolaldehydes
 with olefins to synthesize skipped 1,4-dienes.
;
_journal_issue                   16
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              3870
_journal_page_last               3874
_journal_paper_doi               10.1039/d5ob00173k
_journal_volume                  23
_journal_year                    2025
_chemical_formula_moiety         'C37 H30 O'
_chemical_formula_sum            'C37 H30 O'
_chemical_formula_weight         490.61
_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             2023-11-18
_audit_creation_method
;
Olex2 1.5-ac5-024
(compiled 2022.04.12 svn.rca3783a0 for Rigaku Oxford Diffraction, GUI svn.r6498)
;
_audit_update_record
;
2025-01-25 deposited with the CCDC.	2025-03-13 downloaded from the CCDC.
;
_cell_angle_alpha                80.679(2)
_cell_angle_beta                 76.457(3)
_cell_angle_gamma                81.105(3)
_cell_formula_units_Z            2
_cell_length_a                   7.8705(4)
_cell_length_b                   11.0596(4)
_cell_length_c                   16.4847(4)
_cell_measurement_reflns_used    11561
_cell_measurement_temperature    302.32(10)
_cell_measurement_theta_max      76.0460
_cell_measurement_theta_min      2.7630
_cell_volume                     1366.36(9)
_computing_cell_refinement       'CrysAlisPro 1.171.42.93a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.93a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.93a (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  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      302.32(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.987
_diffrn_measured_fraction_theta_max 0.950
_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    -14.00  16.00   1.00    0.10    --  -46.54  19.00 -30.00   30
  2  \w      2.00  28.00   1.00    0.10    --  -46.54  19.00  60.00   26
  3  \w    -30.00  -4.00   1.00    0.10    --  -46.54  40.00 108.00   26
  4  \w    -23.00  59.00   1.00    0.10    --   46.54 -57.00 -60.00   82
  5  \w    -26.00  28.00   1.00    0.10    --   46.54 -19.00-180.00   54
  6  \w     22.00  47.00   1.00    0.10    --   46.54 -40.00 -45.00   25
  7  \w     72.00 105.00   1.00    0.35    --  104.27 -94.00  90.00   33
  8  \w     74.00 111.00   1.00    0.35    --  104.27-125.00 120.00   37
  9  \w     70.00 106.00   1.00    0.35    --  104.27-105.00 141.64   36
 10  \w     37.00  66.00   1.00    0.35    --  104.27-105.00 141.64   29
 11  \w     35.00  60.00   1.00    0.35    --  104.27-125.00 120.00   25
 12  \w     34.00  62.00   1.00    0.35    --  104.27 -94.00  90.00   28
 13  \w     42.00  88.00   1.00    0.10    --   46.54-125.00 150.00   46
 14  \w     51.00 105.00   1.00    0.35    --  104.27 -94.00 -60.00   54
 15  \w     78.00 111.00   1.00    0.35    --  104.27-125.00-150.00   33
 16  \w     55.00  96.00   1.00    0.35    --  104.27 -94.00-180.00   41
 17  \w     46.00  71.00   1.00    0.35    --  104.27 -61.00 -30.00   25
 18  \w     63.00  97.00   1.00    0.35    --  104.27 -77.00   0.00   34
 19  \w     43.00  73.00   1.00    0.35    --  104.27 -61.00 120.00   30
 20  \w     41.00  68.00   1.00    0.35    --  104.27 -61.00 150.00   27
 21  \w     35.00  68.00   1.00    0.35    --  104.27 -61.00-150.00   33
 22  \w     37.00  65.00   1.00    0.35    --  104.27 -61.00-180.00   28
 23  \w     91.00 119.00   1.00    0.35    --  104.27  15.00-150.00   28
 24  \w    104.00 130.00   1.00    0.35    --  104.27  45.00-180.00   26
 25  \w    137.00 177.00   1.00    0.35    --  104.27  15.00-180.00   40
 26  \w    105.00 176.00   1.00    0.35    --  104.27  40.00 108.00   71
 27  \w     89.00 143.00   1.00    0.35    --  104.27  77.00  30.00   54
 28  \w    125.00 172.00   1.00    0.35    --  104.27  15.00-150.00   47
 29  \w     91.00 132.00   1.00    0.35    --  104.27  15.00-180.00   41
 30  \w     40.00 115.00   1.00    0.10    --   46.54  40.00 108.00   75
 31  \w    -68.00 -39.00   1.00    0.35    -- -102.00  77.00 -90.00   29
 32  \w   -102.00 -72.00   1.00    0.35    -- -102.00  77.00 -90.00   30
 33  \w    -69.00 -44.00   1.00    0.35    -- -102.00  61.00 150.00   25
 34  \w    -60.00 -31.00   1.00    0.35    -- -102.00  61.00  30.00   29
 35  \w    -69.00 -37.00   1.00    0.35    -- -102.00  61.00 -30.00   32
 36  \w   -121.00 -90.00   1.00    0.35    -- -102.00 140.00-122.17   31
 37  \w   -112.00 -37.00   1.00    0.35    -- -102.00 125.00-120.00   75
 38  \w    -74.00 -34.00   1.00    0.35    -- -102.00 125.00 -60.00   40
 39  \w   -112.00 -40.00   1.00    0.35    -- -102.00 125.00   0.00   72
 40  \w   -107.00 -42.00   1.00    0.10    --  -46.54 -40.00 -45.00   65
 41  \w   -167.00-106.00   1.00    0.35    -- -102.00 -40.00 -45.00   61
 42  \w   -172.00-127.00   1.00    0.35    -- -102.00 -61.00 120.00   45
;
_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      0.1050717000
_diffrn_orient_matrix_UB_12      -0.1117715000
_diffrn_orient_matrix_UB_13      0.0423213000
_diffrn_orient_matrix_UB_21      -0.1667797000
_diffrn_orient_matrix_UB_22      -0.0660217000
_diffrn_orient_matrix_UB_23      0.0283122000
_diffrn_orient_matrix_UB_31      0.0478284000
_diffrn_orient_matrix_UB_32      -0.0581262000
_diffrn_orient_matrix_UB_33      -0.0825202000
_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  0.0353
_diffrn_reflns_av_unetI/netI     0.0349
_diffrn_reflns_Laue_measured_fraction_full 0.987
_diffrn_reflns_Laue_measured_fraction_max 0.950
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            15670
_diffrn_reflns_point_group_measured_fraction_full 0.987
_diffrn_reflns_point_group_measured_fraction_max 0.950
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.266
_diffrn_reflns_theta_min         2.781
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.534
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.84572
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.93a (Rigaku Oxford Diffraction, 2023)
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    1.192
_exptl_crystal_description       block
_exptl_crystal_F_000             520
_exptl_crystal_size_max          0.24
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.13
_refine_diff_density_max         0.220
_refine_diff_density_min         -0.229
_refine_diff_density_rms         0.031
_refine_ls_extinction_coef       0.0135(16)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.081
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     333
_refine_ls_number_reflns         5419
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.081
_refine_ls_R_factor_all          0.0528
_refine_ls_R_factor_gt           0.0480
_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^)+(0.0662P)^2^+0.2437P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1323
_refine_ls_wR_factor_ref         0.1351
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4926
_reflns_number_total             5419
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ob00173k2.cif
_cod_data_source_block           zhuht_1118_auto
_cod_depositor_comments
'Adding full bibliography for 7160406--7160410.cif.'
_cod_original_cell_volume        1366.38(9)
_cod_database_code               7160408
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.934
_shelx_estimated_absorpt_t_min   0.882
_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:
 C1(H1), C8(H8)
2.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C6(H6), C10(H10), C13(H13), C14(H14), C15(H15),
 C16(H16), C17(H17), C19(H19), C20(H20), C21(H21), C22(H22), C23(H23), C26(H26),
  C27(H27), C28(H28), C29(H29), C30(H30), C32(H32), C33(H33), C34(H34),
 C35(H35), C36(H36)
2.c Fitted hexagon refined as free rotating group:
 C19(C20,C21,C22,C23,C18)
2.d Idealised Me refined as rotating group:
 C37(H37A,H37B,H37C)
;
_shelx_res_checksum              42790
_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 1.432
_oxdiff_exptl_absorpt_empirical_full_min 0.622