Enantioselective construction of substituted pyridine and a seven-membered carbocyclic skeleton: biomimetic synthesis of (-)-rupestine D, (-)-guaipyridine, (-)-epiguaipyridine, and (-)-cananodine and their stereoisomers.
Zhang, Cun; Wang, Bianlin; Aibibula, Paruke; Zhao, Jiangyu; Aisa, Haji Akber; Organic & biomolecular chemistry 19 (2021) 7081–7084; doi:10.1039/d1ob01299a

data_7158217
_publ_section_title
;
 Enantioselective construction of substituted pyridine and a
 seven-membered carbocyclic skeleton: biomimetic synthesis of
 (-)-rupestine D, (-)-guaipyridine, (-)-epiguaipyridine, and
 (-)-cananodine and their stereoisomers.
;
_journal_issue                   32
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              7081
_journal_page_last               7084
_journal_paper_doi               10.1039/d1ob01299a
_journal_volume                  19
_journal_year                    2021
_chemical_absolute_configuration rmad
_chemical_formula_moiety         'C14 H19 N O'
_chemical_formula_sum            'C14 H19 N O'
_chemical_formula_weight         217.30
_chemical_melting_point          378.65
_chemical_name_common            'Rupestine D'
_chemical_name_systematic        'Rupestine D'
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_block_doi                 10.5517/ccdc.csd.cc27zgyn
_audit_creation_date             2020-12-07
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2021-05-20 deposited with the CCDC.	2021-07-28 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 101.617(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   4.9824(2)
_cell_length_b                   11.7685(5)
_cell_length_c                   10.6674(5)
_cell_measurement_reflns_used    9545
_cell_measurement_temperature    150
_cell_measurement_theta_max      74.293
_cell_measurement_theta_min      3.756
_cell_volume                     612.67(5)
_computing_cell_refinement       'SAINT V8.40A (?, 2016)'
_computing_data_reduction        'SAINT V8.40A (?, 2016)'
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      150.0
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Bruker D8 VENTURE'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0486
_diffrn_reflns_av_unetI/netI     0.0398
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       5
_diffrn_reflns_limit_h_min       -5
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            10051
_diffrn_reflns_point_group_measured_fraction_full 0.988
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         68.216
_diffrn_reflns_theta_min         4.231
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.571
_exptl_absorpt_correction_T_max  0.7538
_exptl_absorpt_correction_T_min  0.5850
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1584 before and 0.0844 after correction. The Ratio of minimum to maximum transmission is 0.7761. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.178
_exptl_crystal_description       block
_exptl_crystal_F_000             236
_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent: PE'
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.152
_refine_diff_density_min         -0.188
_refine_diff_density_rms         0.040
_refine_ls_abs_structure_details
;
 Flack x determined using 942 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.01(15)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.073
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     148
_refine_ls_number_reflns         2194
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.073
_refine_ls_R_factor_all          0.0395
_refine_ls_R_factor_gt           0.0383
_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^)+(0.0536P)^2^+0.0997P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1012
_refine_ls_wR_factor_ref         0.1025
_reflns_Friedel_coverage         0.882
_reflns_Friedel_fraction_full    0.977
_reflns_Friedel_fraction_max     0.976
_reflns_number_gt                2137
_reflns_number_total             2194
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1ob01299a2.cif
_cod_data_source_block           cu_220201016_0m
_cod_depositor_comments
'Adding full bibliography for 7158216--7158217.cif.'
_cod_database_code               7158217
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.972
_shelx_estimated_absorpt_t_min   0.919
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C11(H11), C8(H8)
2.b Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C9(H9A,H9B), C10(H10A,H10B)
2.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3)
2.d Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), C6(H6A,H6B,H6C), C14(H14A,H14B,H14C)
;
_olex2_submission_special_instructions 'No special instructions were received'