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_1547515
_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         'C21 H26 N2 O2'
_chemical_formula_sum            'C21 H26 N2 O2'
_chemical_formula_weight         338.44
_chemical_name_systematic
(R)-3a-ethyl-(methoxymethyl)-1,2,3,3a,4,5-hexahydrobenzo[2,3]azonino[6,5,4-hi]indolizin-6(7H)-one
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2016-10-24
_audit_creation_method
;
Olex2 1.2
(compiled 2016.09.09 svn.r3337 for OlexSys, GUI svn.r5227)
;
_cell_angle_alpha                90
_cell_angle_beta                 98.124(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.3072(7)
_cell_length_b                   23.509(2)
_cell_length_c                   8.9287(8)
_cell_measurement_reflns_used    7046
_cell_measurement_temperature    100.0(1)
_cell_measurement_theta_max      33.21
_cell_measurement_theta_min      2.62
_cell_volume                     1726.2(3)
_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 0.999
_diffrn_measured_fraction_theta_max 0.994
_diffrn_measurement_device       'kappa-stage diffractometer'
_diffrn_measurement_device_type  'Bruker Apex2 Duo (Mo)'
_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  0.0329
_diffrn_reflns_av_unetI/netI     0.0322
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -5
_diffrn_reflns_limit_k_max       35
_diffrn_reflns_limit_k_min       -36
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            26977
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         33.328
_diffrn_reflns_theta_min         2.462
_diffrn_source                   'sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.084
_exptl_absorpt_correction_T_max  0.7465
_exptl_absorpt_correction_T_min  0.7099
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.0440 before and 0.0415 after correction.
The Ratio of minimum to maximum transmission is 0.9510.
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    1.302
_exptl_crystal_description       block
_exptl_crystal_F_000             728
_exptl_crystal_size_max          0.24
_exptl_crystal_size_mid          0.105
_exptl_crystal_size_min          0.09
_refine_diff_density_max         0.508
_refine_diff_density_min         -0.245
_refine_diff_density_rms         0.054
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.020
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     228
_refine_ls_number_reflns         6646
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.020
_refine_ls_R_factor_all          0.0601
_refine_ls_R_factor_gt           0.0434
_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^)+(0.0646P)^2^+0.3477P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1095
_refine_ls_wR_factor_ref         0.1191
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5217
_reflns_number_total             6646
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ol7b02619_si_002.cif
_cod_data_source_block           mo_ca201016_1_1_0m
_cod_depositor_comments
'Adding full bibliography for 1547514--1547515.cif.'
_cod_database_code               1547515
_shelx_estimated_absorpt_t_max   0.992
_shelx_estimated_absorpt_t_min   0.980
_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 Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C6(H6A,H6B), C12(H12A,H12B), C13(H13A,H13B), C15(H15A,H15B),
 C17(H17A,H17B), C18(H18A,H18B)
2.b Aromatic/amide H refined with riding coordinates:
 C8(H8), C9(H9), C10(H10), C11(H11), C20(H20), C21(H21)
2.c Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C16(H16A,H16B,H16C)
;
_shelx_res_checksum              20792
_shelx_hkl_checksum              26476
_shelx_shelxl_version_number     2014/7
_olex2_date_sample_data_collection 2016-10-21
_olex2_date_sample_submission    2016-10-20
_olex2_submission_original_sample_id ca201016_1_1
_olex2_submission_special_instructions 'No special instructions were received'