Total Synthesis of (-)-Rhazinilam and Formal Synthesis of (+)-Eburenine and (+)-Aspidospermidine: Asymmetric Cu-Catalyzed Propargylic Substitution.
Shemet, Andrej; Carreira, Erick M.; Organic letters 19 (2017) 5529–5532; doi:10.1021/acs.orglett.7b02619

data_1547514
_publ_section_title
;
 Total Synthesis of (-)-Rhazinilam and Formal Synthesis of (+)-Eburenine
 and (+)-Aspidospermidine: Asymmetric Cu-Catalyzed Propargylic
 Substitution.
;
_journal_issue                   20
_journal_name_full               'Organic letters'
_journal_page_first              5529
_journal_page_last               5532
_journal_paper_doi               10.1021/acs.orglett.7b02619
_journal_volume                  19
_journal_year                    2017
_chemical_formula_moiety         'C13 H15 N O2'
_chemical_formula_sum            'C13 H15 N O2'
_chemical_formula_weight         217.26
_chemical_name_systematic
'3-(8-ethyl-5,6,7,8-tetrahydroindolizin-8-yl)propiolic acid'
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2016-09-30
_audit_creation_method
;
Olex2 1.2
(compiled 2016.09.09 svn.r3337 for OlexSys, GUI svn.r5227)
;
_cell_angle_alpha                108.041(2)
_cell_angle_beta                 101.319(2)
_cell_angle_gamma                98.946(2)
_cell_formula_units_Z            2
_cell_length_a                   7.3581(6)
_cell_length_b                   9.0853(7)
_cell_length_c                   9.4911(7)
_cell_measurement_reflns_used    4178
_cell_measurement_temperature    100.0(1)
_cell_measurement_theta_max      30.54
_cell_measurement_theta_min      2.71
_cell_volume                     575.42(8)
_computing_cell_refinement       'Bruker SAINT'
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'Bruker SAINT'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XS (Sheldrick, 2008)'
_diffrn_ambient_temperature      100.0(1)
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 8.33
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device       'kappa-stage diffractometer'
_diffrn_measurement_device_type  'Bruker Kappa Apex2 Duo'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'focusing graphite'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0273
_diffrn_reflns_av_unetI/netI     0.0254
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            13500
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         30.552
_diffrn_reflns_theta_min         2.337
_diffrn_source                   'sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.085
_exptl_absorpt_correction_T_max  0.7461
_exptl_absorpt_correction_T_min  0.7107
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.0439 before and 0.0389 after correction.
The Ratio of minimum to maximum transmission is 0.9526.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.254
_exptl_crystal_description       block
_exptl_crystal_F_000             232
_exptl_crystal_size_max          0.21
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.516
_refine_diff_density_min         -0.227
_refine_diff_density_rms         0.051
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.026
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     149
_refine_ls_number_reflns         3523
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.026
_refine_ls_R_factor_all          0.0565
_refine_ls_R_factor_gt           0.0442
_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^)+(0.0525P)^2^+0.2711P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1091
_refine_ls_wR_factor_ref         0.1175
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2900
_reflns_number_total             3523
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ol7b02619_si_003.cif
_cod_data_source_block           mo_ca220916_1_1_0m
_cod_depositor_comments
'Adding full bibliography for 1547514--1547515.cif.'
_cod_database_code               1547514
_shelx_estimated_absorpt_t_max   0.993
_shelx_estimated_absorpt_t_min   0.982
_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
 O2-H2
 0.91 with sigma of 0.01
3.a Secondary CH2 refined with riding coordinates:
 C5(H5A,H5B), C13(H13A,H13B), C11(H11A,H11B), C12(H12A,H12B)
3.b Aromatic/amide H refined with riding coordinates:
 C8(H8), C9(H9), C10(H10)
3.c Idealised Me refined as rotating group:
 C6(H6A,H6B,H6C)
;
_shelx_res_checksum              37612
_shelx_hkl_checksum              47885
_shelx_shelxl_version_number     2014/7
_olex2_date_sample_data_collection 2016-09-23
_olex2_date_sample_submission    2016-09-23
_olex2_submission_original_sample_id ca220916_1_1
_olex2_submission_special_instructions 'No special instructions were received'