Asymmetric Total Synthesis of Arcutinidine, Arcutinine, and Arcutine.
Zhou, Shupeng; Xia, Kaifu; Leng, Xuebing; Li, Ang; Journal of the American Chemical Society 141 (2019) 13718–13723; doi:10.1021/jacs.9b05818

data_4128871
_publ_section_title
;
 Asymmetric Total Synthesis of Arcutinidine, Arcutinine, and Arcutine.
;
_journal_issue                   35
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              13718
_journal_page_last               13723
_journal_paper_doi               10.1021/jacs.9b05818
_journal_volume                  141
_journal_year                    2019
_chemical_absolute_configuration rmad
_chemical_formula_moiety         'C25 H35 N O3'
_chemical_formula_sum            'C25 H35 N O3'
_chemical_formula_weight         397.54
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-06-20
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            12
_cell_length_a                   11.5553(5)
_cell_length_b                   21.4201(9)
_cell_length_c                   26.2735(12)
_cell_measurement_reflns_used    9790
_cell_measurement_temperature    170(2)
_cell_measurement_theta_max      53.10
_cell_measurement_theta_min      2.93
_cell_volume                     6503.1(5)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_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      169.96
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Bruker D8 Venture'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           GaK\a
_diffrn_radiation_wavelength     1.34139
_diffrn_reflns_av_R_equivalents  0.0696
_diffrn_reflns_av_unetI/netI     0.0519
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            55555
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        53.594
_diffrn_reflns_theta_max         54.994
_diffrn_reflns_theta_min         2.927
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.398
_exptl_absorpt_correction_T_max  0.7508
_exptl_absorpt_correction_T_min  0.5003
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1328 before and 0.0863 after correction. The Ratio of minimum to maximum transmission is 0.6664. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.218
_exptl_crystal_description       needle
_exptl_crystal_F_000             2592
_exptl_crystal_size_max          0.08
_exptl_crystal_size_mid          0.02
_exptl_crystal_size_min          0.01
_refine_diff_density_max         0.810
_refine_diff_density_min         -0.335
_refine_diff_density_rms         0.089
_refine_ls_abs_structure_details
;
 Flack x determined using 3035 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.12(12)
_refine_ls_extinction_coef       0.0063(11)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2016/6 (Sheldrick 2016)'
_refine_ls_goodness_of_fit_ref   1.130
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     835
_refine_ls_number_reflns         12360
_refine_ls_number_restraints     71
_refine_ls_restrained_S_all      1.132
_refine_ls_R_factor_all          0.1252
_refine_ls_R_factor_gt           0.1000
_refine_ls_shift/su_max          0.013
_refine_ls_shift/su_mean         0.002
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2648
_refine_ls_wR_factor_ref         0.2954
_reflns_Friedel_coverage         0.813
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.997
_reflns_number_gt                8779
_reflns_number_total             12360
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b05818_si_006.cif
_cod_data_source_block           mj19419_0m
_cod_database_code               4128871
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.996
_shelx_estimated_absorpt_t_min   0.969
_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, All O(H) groups
2. Restrained distances
 C22B-C21B = C22B-C23B = C22B-C24B
 1.53 with sigma of 0.02
 C27B-C26B
 1.53 with sigma of 0.02
 C24B-C25B
 1.53 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C21B \\sim C23B \\sim C24B \\sim C25B \\sim C26B \\sim C27B \\sim C28B: within
2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C28B \\sim C29B: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02
4. Others
 Fixed Sof: C22B(0.5) H22B(0.5) C23B(0.5) H23A(0.5) H23B(0.5) H23C(0.5)
 C24B(0.5) H24A(0.5) H24B(0.5) C25B(0.5) H25A(0.5) H25B(0.5) H25C(0.5)
 C26B(0.5) H26B(0.5) C27B(0.5) H27A(0.5) H27B(0.5) H27C(0.5) C28B(0.5)
 H28A(0.5) H28B(0.5) C29B(0.5) H29A(0.5) H29B(0.5) H29C(0.5)
5.a Ternary CH refined with riding coordinates:
 C9(H9), C13(H13), C15(H15), C18(H18), C22(H22), C9A(H9A), C13A(H13A),
 C15A(H15A), C18A(H18A), C22A(H22A), C9B(H9B), C13B(H13B), C15B(H15B),
 C18B(H18B), C22B(H22B), C26B(H26B)
5.b Secondary CH2 refined with riding coordinates:
 C1(H1A,H1C), C3(H3A,H3B), C4(H4A,H4B), C5(H5A,H5B), C11(H11C,H11D), C12(H12C,
 H12D), C14(H14C,H14D), C16(H16C,H16D), C24(H24C,H24D), C1A(H1AB,H1AC),
 C3A(H3AA,H3AB), C4A(H4AA,H4AB), C5A(H5AA,H5AB), C11A(H11E,H11F), C12A(H12E,
 H12F), C14A(H14E,H14F), C16A(H16E,H16F), C24A(H24E,H24F), C1B(H1BA,H1BB),
 C3B(H3BA,H3BB), C4B(H4BA,H4BB), C5B(H5BA,H5BB), C11B(H11A,H11B), C12B(H12A,
 H12B), C14B(H14A,H14B), C16B(H16A,H16B), C24B(H24A,H24B), C28B(H28A,H28B)
5.c X=CH2 refined with riding coordinates:
 C19(H19C,H19D), C19A(H19E,H19F), C19B(H19A,H19B)
5.d Idealised Me refined as rotating group:
 C20(H20D,H20E,H20F), C23(H23D,H23E,H23F), C25(H25D,H25E,H25F), C20A(H20G,H20H,
 H20I), C23A(H23G,H23H,H23I), C25A(H25G,H25H,H25I), C20B(H20A,H20B,H20C),
 C23B(H23A,H23B,H23C), C25B(H25A,H25B,H25C), C27B(H27A,H27B,H27C), C29B(H29A,
 H29B,H29C)
5.e Idealised tetrahedral OH refined as rotating group:
 O1(H1), O1A(H1AA), O1B(H1B)
;
_shelx_res_checksum              22225
_shelx_hkl_checksum              36133
_olex2_submission_special_instructions 'No special instructions were received'