Ruthenium-catalysed isomerisation-methylenation of allyl alcohols with methanol: a one-pot synthesis of substituted pyridines.
Biswal, Priyabrata; Pullarat, Sanu Siyad; Samser, Shaikh; Aradhyula, Basava Punna Rao; Chandrasekhar, Vadapalli; Venkatasubbaiah, Krishnan; Organic & biomolecular chemistry 23 (2025) 6931–6937; doi:10.1039/d5ob00881f

data_7160603
_publ_section_title
;
 Ruthenium-catalysed isomerisation-methylenation of allyl alcohols with
 methanol: a one-pot synthesis of substituted pyridines.
;
_journal_issue                   29
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              6931
_journal_page_last               6937
_journal_paper_doi               10.1039/d5ob00881f
_journal_volume                  23
_journal_year                    2025
_chemical_formula_moiety         'C31 H23 F2 N'
_chemical_formula_sum            'C31 H23 F2 N'
_chemical_formula_weight         447.50
_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             2024-04-24
_audit_creation_method
;
Olex2 1.5-ac5-021
(compiled 2022.02.15 svn.rf212a0ae for Rigaku Oxford Diffraction, GUI svn.r6439)
;
_audit_update_record
;
2025-04-11 deposited with the CCDC.	2025-06-23 downloaded from the CCDC.
;
_cell_angle_alpha                90.043(5)
_cell_angle_beta                 104.592(5)
_cell_angle_gamma                106.186(5)
_cell_formula_units_Z            2
_cell_length_a                   9.4134(5)
_cell_length_b                   10.6542(7)
_cell_length_c                   12.1372(7)
_cell_measurement_reflns_used    7897
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      30.6310
_cell_measurement_theta_min      3.5320
_cell_volume                     1128.01(12)
_computing_cell_refinement       'CrysAlisPro 1.171.42.52a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.52a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.52a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5-ac5-021 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-ac5-021 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2014/7 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_detector_type            'Pilatus 200K'
_diffrn_measured_fraction_theta_full 0.997
_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     23.00  72.00   0.50   14.03    --    3.51-156.00-163.00   98
  2  \w      1.00  51.00   0.50   14.03    --    3.51-119.00  -7.00  100
  3  \w     -8.00  66.00   0.50   14.03    --    3.51  57.00   0.00  148
  4  \w    -63.00   7.00   0.50   14.03    --    3.51 -37.00-150.00  140
  5  \w    -42.00  19.00   0.50   14.03    --   -4.14 -77.00  60.00  122
  6  \w    -42.00  19.00   0.50   14.03    --   -4.14 -77.00 -30.00  122
  7  \w    -15.00  29.00   0.50   14.03    --   -4.14 -99.00-180.00   88
  8  \w    -11.00  26.00   0.50   14.03    --   -4.14 -99.00-120.00   74
  9  \w    -22.00  19.00   0.50   14.03    --   -4.14  77.00 -90.00   82
 10  \w     24.00  50.00   0.50   14.03    --   -4.14  37.00 -90.00   52
 11  \w     -7.00  55.00   0.50   14.03    --   -4.14  37.00-180.00  124
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'SuperNova, Dual, Cu at home/near, Pilatus 200K'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0582011000
_diffrn_orient_matrix_UB_12      0.0310474000
_diffrn_orient_matrix_UB_13      0.0494789000
_diffrn_orient_matrix_UB_21      -0.0363457000
_diffrn_orient_matrix_UB_22      -0.0457335000
_diffrn_orient_matrix_UB_23      0.0339872000
_diffrn_orient_matrix_UB_31      0.0436279000
_diffrn_orient_matrix_UB_32      -0.0421687000
_diffrn_orient_matrix_UB_33      -0.0080541000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0986
_diffrn_reflns_av_unetI/netI     0.0595
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            16731
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        24.998
_diffrn_reflns_theta_max         24.998
_diffrn_reflns_theta_min         3.374
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.087
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.40941
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.52a (Rigaku Oxford Diffraction, 2022)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear yellowish white'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   yellowish
_exptl_crystal_colour_primary    white
_exptl_crystal_density_diffrn    1.318
_exptl_crystal_description       block
_exptl_crystal_F_000             468
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.635
_refine_diff_density_min         -0.338
_refine_diff_density_rms         0.110
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.065
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     307
_refine_ls_number_reflns         3975
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.065
_refine_ls_R_factor_all          0.0766
_refine_ls_R_factor_gt           0.0691
_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^)+(0.1396P)^2^+0.0744P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1841
_refine_ls_wR_factor_ref         0.1916
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3360
_reflns_number_total             3975
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ob00881f2.cif
_cod_data_source_block           kv-pbb-396-t_auto
_cod_depositor_comments          'Adding full bibliography for 7160603.cif.'
_cod_original_cell_volume        1128.00(12)
_cod_database_code               7160603
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         ' C H N F'
_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:
 C19(H19A,H19B), C27(H27A,H27B)
2.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C8(H8), C18(H18), C12(H12), C11(H11), C29(H29), C9(H9), C10(H10),
 C33(H33), C30(H30), C14(H14), C24(H24), C17(H17), C21(H21), C32(H32), C25(H25),
  C15(H15), C22(H22), C16(H16)
;
_shelx_res_checksum              25530
_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 2.913
_oxdiff_exptl_absorpt_empirical_full_min 0.270