Application of a Raney-cobalt-mediated tandem reductive cyclization protocol to total syntheses of the Aspidosperma alkaloids (±)-limaspermidine and (±)-1-acetylaspidoalbidine.
Tan, Shen H.; Banwell, Martin G.; Willis, Anthony C.; Reekie, Tristan A.; Organic letters 14 (2012) 5621–5623; doi:10.1021/ol3026846

data_1516067
_publ_section_title
;
 Application of a Raney-cobalt-mediated tandem reductive cyclization
 protocol to total syntheses of the Aspidosperma alkaloids
 (+-)-limaspermidine and (+-)-1-acetylaspidoalbidine.
;
_journal_issue                   22
_journal_name_full               'Organic letters'
_journal_page_first              5621
_journal_page_last               5623
_journal_paper_doi               10.1021/ol3026846
_journal_volume                  14
_journal_year                    2012
_chemical_compound_source        local
_chemical_formula_moiety         'C19 H25 N3 O, C H4 O'
_chemical_formula_sum            'C20 H29 N3 O2'
_chemical_formula_weight         343.47
_space_group_IT_number           14
_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             11-09-16
_audit_creation_method           CRYSTALS_ver_14.11
_audit_update_record
;
2011-09-16 - Report on C20 H29 N3 O2
             by Anthony C. Willis
             for  Hui Xian (Shen) Tan and Martin Banwell

2011-09-16 - passes most checkcif tests 

;
_cell_angle_alpha                90
_cell_angle_beta                 109.2418(9)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.8836(1)
_cell_length_b                   10.3003(2)
_cell_length_c                   15.9702(2)
_cell_measurement_reflns_used    25821
_cell_measurement_temperature    200
_cell_measurement_theta_max      30
_cell_measurement_theta_min      2.6
_cell_volume                     1845.62(5)
_computing_cell_refinement       'DENZO/SCALEPACK (Otwinowski & Minor, 1997)'
_computing_data_collection       'COLLECT (Nonius, 2001).'
_computing_data_reduction        'DENZO/SCALEPACK (Otwinowski & Minor, 1997)'
_computing_molecular_graphics
;  
ORTEP-II (Johnson 1976) in teXsan (MSC, 1992-1997) 
;
_computing_publication_material  'CRYSTALS (Betteridge et al., 2003)'
_computing_structure_refinement  'CRYSTALS (Betteridge et al., 2003)'
_computing_structure_solution    'SIR92 (Altomare et al., 1994)'
_diffrn_ambient_temperature      200
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device       Area
_diffrn_measurement_device_type  'Nonius KappaCCD'
_diffrn_measurement_method       ' \f and \w scans with CCD '
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.032
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            49073
_diffrn_reflns_theta_full        30.035
_diffrn_reflns_theta_max         30.035
_diffrn_reflns_theta_min         2.684
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.081
_exptl_absorpt_correction_T_max  0.990
_exptl_absorpt_correction_T_min  0.969
_exptl_absorpt_correction_type   integration
_exptl_absorpt_process_details
;
via Gaussian method (Coppens, 1970) implemented in maXus (2000)
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.236
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             744
_exptl_crystal_size_max          0.480
_exptl_crystal_size_mid          0.260
_exptl_crystal_size_min          0.160
_refine_diff_density_max         0.31
_refine_diff_density_min         -0.22
_refine_ls_extinction_method     None
_refine_ls_goodness_of_fit_ref   0.9957
_refine_ls_hydrogen_treatment    refxyz
_refine_ls_matrix_type           full
_refine_ls_number_parameters     313
_refine_ls_number_reflns         5404
_refine_ls_number_restraints     9
_refine_ls_R_factor_all          0.0478
_refine_ls_R_factor_gt           0.0408
_refine_ls_shift/su_max          0.0312201
_refine_ls_shift/su_mean         0.0006689
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
;
 Method= Modified Sheldrick 
 w=1/[\s^2^(F^2^) + ( 0.06P)^2^ + 0.52P] 
 ,where P=(max(Fo^2^,0) + 2Fc^2^)/3 
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_all         0.1124
_refine_ls_wR_factor_gt          0.1070
_refine_ls_wR_factor_ref         0.1124
_reflns_limit_h_max              15
_reflns_limit_h_min              -16
_reflns_limit_k_max              14
_reflns_limit_k_min              0
_reflns_limit_l_max              22
_reflns_limit_l_min              0
_reflns_number_gt                4683
_reflns_number_total             5404
_reflns_threshold_expression     I>2.0\s(I)
_oxford_diffrn_Wilson_B_factor   2.17
_oxford_diffrn_Wilson_scale      0.62
_oxford_refine_ls_r_factor_ref   0.0478
_oxford_refine_ls_scale          1.352(6)
_oxford_reflns_number_all        5404
_oxford_reflns_threshold_expression_ref I>-10.0\s(I)
_oxford_structure_analysis_title '9161144 ban1138'
_cod_data_source_file            ol3026846_si_003.cif
_cod_data_source_block           ban1138
_cod_depositor_comments
;
The following automatic conversions were performed:

'_symmetry_cell_setting' value 'Monoclinic' changed to 'monoclinic'
according to
/usr/data/users/saulius/automatic-downloads/retrospective/ACS/lib/dictionaries/cif_core.dic
dictionary named 'cif_core.dic' version 2.4.2 from 2011-04-26.

Automatic conversion script
Id: cif_fix_values 2281 2013-09-26 08:29:07Z andrius 
;
_cod_original_sg_symbol_H-M      'P 1 21/c 1 '
_cod_database_code               1516067
_iucr_refine_instruction_details_constraints
;
BLOCK 
CONT SCALE 
CONT N    (    1 ,X'S,U'S)  UNTIL C    (   25 ) 
CONT H    (   11 ,X'S)  UNTIL H    (  253 ) 
END                                                                             
;
_iucr_refine_instruction_details_restraints
;
NO 
REM   HREST   START (DO NOT REMOVE THIS LINE) 
REM NO H   NO #H U MULT DIST 
REM C-H 
REM >4           1.5    .96 DISORDER 
REM 1      1     1.2    .93 C C-H (ACETYLENE) 
REM 1      2     1.2    .93 C-C(H)-C 
REM 1      3     1.2    .98 (C)3-C-H 
REM 2      1     1.2    .93 C=C-H(2) 
REM 2      2     1.2    .97 (C)2-C-(H)2 
REM 3      1     1.5    .96 C-C-(H)3 
REM N-H 
REM >4           1.5    .89 DISORDER 
REM 1      1     1.2    .86 N-N/H 
REM 1      2     1.2    .86 (C)2-N-H 
REM 1      3     1.2    .89 (C)3-N-H 
REM 2      1     1.2    .86 C-N-(H)2 
REM 2      2     1.2    .89 (C)2-N-(H)2 
REM 3      1     1.2    .89 C-H-(H)3 
REM O-H 
REM 1      1     1.5    .82 O-H 
REM 
REM DIST      ESD = 0.02 
REM VIB       ESD = 0.002 
REM ANGLE     ESD = 2.0 
REM            3 H ON SP 3 
DIST 0.96, 0.02 = 
CONT C ( 25) TO H(251) 
CONT C ( 25) TO H(252) 
CONT C ( 25) TO H(253) 
REST 0.094, 0.002 = H(251,U[ISO]) 
REST 0.094, 0.002 = H(252,U[ISO]) 
REST 0.094, 0.002 = H(253,U[ISO]) 
ANGLE 109.54, 2.0 = 
CONT O(24) TO C ( 25) TO H(251) 
CONT O(24) TO C ( 25) TO H(252) 
CONT O(24) TO C ( 25) TO H(253) 
ANGLE 0.0, 2.0 = MEAN H(251) TO C ( 25) TO H(252) 
CONT H(251) TO C ( 25) TO H(253) 
CONT H(252) TO C ( 25) TO H(253) 
REM   HREST   END (DO NOT REMOVE THIS LINE) 
END                                                                             
;