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_7160409
_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         'C36 H24 O2'
_chemical_formula_sum            'C36 H24 O2'
_chemical_formula_weight         488.55
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-10-13
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2025-01-25 deposited with the CCDC.	2025-03-13 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 106.5380(10)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   16.0351(2)
_cell_length_b                   19.3964(2)
_cell_length_c                   17.3183(2)
_cell_measurement_reflns_used    17039
_cell_measurement_temperature    291(2)
_cell_measurement_theta_max      75.7770
_cell_measurement_theta_min      2.6940
_cell_volume                     5163.56(11)
_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 (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      291(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.943
_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    -73.00 -25.75   0.75    1.50    -- -100.00  61.00 150.00   63
  2  \w    -54.00 -25.50   0.75    1.50    -- -100.00  45.00 150.00   38
  3  \w    -55.00 -25.75   0.75    1.50    -- -100.00  45.00 120.00   39
  4  \w    -55.00 -25.75   0.75    1.50    -- -100.00  45.00  90.00   39
  5  \w    -55.00 -25.75   0.75    1.50    -- -100.00  45.00  60.00   39
  6  \w    -45.00  31.50   0.75    0.50    --  -45.30  37.00  60.00  102
  7  \w     27.00  62.25   0.75    0.50    --   45.30  57.00  30.00   47
  8  \w     72.00 118.50   0.75    0.50    --   45.30  57.00  30.00   62
  9  \w     76.00 102.25   0.75    0.50    --   45.30 135.00  95.00   35
 10  \w     98.00 123.50   0.75    1.50    --  109.64 135.00  95.00   34
 11  \w     70.00 131.50   0.75    1.50    --  109.64 134.00 -83.00   82
 12  \w     70.00  96.25   0.75    0.50    --   45.30 134.00 -83.00   35
 13  \w    112.00 158.50   0.75    1.50    --  109.64  45.00-150.00   62
 14  \w     52.00  99.25   0.75    1.50    --  109.64 -77.00-180.00   63
 15  \w     73.00  99.25   0.75    1.50    --  109.64 -77.00-150.00   35
 16  \w     27.00  94.50   0.75    0.50    --   45.30-134.00-151.00   90
 17  \w     41.00  74.00   0.75    0.50    --   45.30-135.00  29.00   44
 18  \w     53.00  78.50   0.75    1.50    --  109.64-135.00  29.00   34
 19  \w     38.00  72.50   0.75    1.50    --  109.64 -94.00  60.00   46
 20  \w     54.00  79.50   0.75    1.50    --  109.64-134.00-151.00   34
 21  \w     68.00 111.50   0.75    1.50    --  109.64-125.00-120.00   58
 22  \w   -118.00 -65.50   0.75    1.50    -- -100.00 135.00  95.00   70
 23  \w   -115.00 -70.75   0.75    1.50    -- -100.00 134.00 -83.00   59
 24  \w   -112.00 -34.00   0.75    1.50    -- -100.00 125.00-120.00  104
 25  \w   -160.00 -91.75   0.75    1.50    -- -100.00 -94.00  90.00   91
 26  \w   -163.00 -91.75   0.75    1.50    -- -100.00 -61.00 -60.00   95
 27  \w   -139.00 -91.00   0.75    1.50    -- -100.00-134.00-151.00   64
 28  \w   -171.00 -81.75   0.75    1.50    -- -100.00-125.00-120.00  119
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'ROD, Synergy Custom system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0462916000
_diffrn_orient_matrix_UB_12      -0.0363579000
_diffrn_orient_matrix_UB_13      -0.0797984000
_diffrn_orient_matrix_UB_21      0.0243824000
_diffrn_orient_matrix_UB_22      -0.0705994000
_diffrn_orient_matrix_UB_23      0.0409509000
_diffrn_orient_matrix_UB_31      -0.0854289000
_diffrn_orient_matrix_UB_32      -0.0004113000
_diffrn_orient_matrix_UB_33      0.0239713000
_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  0.0382
_diffrn_reflns_av_unetI/netI     0.0356
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.943
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            20264
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.943
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.849
_diffrn_reflns_theta_min         3.669
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.598
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.63288
_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 dark yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.257
_exptl_crystal_description       block
_exptl_crystal_F_000             2048
_exptl_crystal_size_max          0.23
_exptl_crystal_size_mid          0.21
_exptl_crystal_size_min          0.14
_refine_diff_density_max         0.214
_refine_diff_density_min         -0.193
_refine_diff_density_rms         0.047
_refine_ls_extinction_coef       0.00043(10)
_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   1.036
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     345
_refine_ls_number_reflns         5135
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.036
_refine_ls_R_factor_all          0.0580
_refine_ls_R_factor_gt           0.0514
_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^)+(0.0762P)^2^+1.5336P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1397
_refine_ls_wR_factor_ref         0.1456
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4391
_reflns_number_total             5135
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ob00173k2.cif
_cod_data_source_block           zhu_1014_auto
_cod_depositor_comments
'Adding full bibliography for 7160406--7160410.cif.'
_cod_database_code               7160409
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.921
_shelx_estimated_absorpt_t_min   0.875
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All O(H) groups
2.a Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C6(H6), C12(H12), C13(H13), C14(H14), C15(H15),
 C20(H20), C21(H21), C22(H22), C23(H23), C24(H24), C26(H26), C27(H27), C28(H28),
  C29(H29), C30(H30), C32(H32), C33(H33), C34(H34), C35(H35), C36(H36)
2.b Idealised tetrahedral OH refined as rotating group:
 O2(H2)
;
_shelx_res_checksum              94603
_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 2.869
_oxdiff_exptl_absorpt_empirical_full_min 0.347