A Raney-Cobalt-Mediated Tandem Reductive Cyclization Route to the 1,5-Methanoazocino[4,3-b]indole Framework of the Uleine and Strychnos Alkaloids
Tristan A. Reekie; Martin G. Banwell; Anthony C. Willis; Journal of Organic Chemistry 77 (2012) 10773–10781; doi:10.1021/jo302132d

data_4027772
_publ_contact_author_address
;
Research School of Chemistry,
Australian National University,
Canberra, A. C. T. 0200, Australia
;
_publ_contact_author_email       'mgb@rsc.anu.edu.au '
_publ_contact_author_fax         ' 61 2 6125 8114 '
_publ_contact_author_name        'Martin G. Banwell'
_publ_contact_author_phone       ' 61 2 6125 8202 '
_publ_section_title
;
 A Raney-Cobalt-Mediated Tandem Reductive Cyclization Route to the
 1,5-Methanoazocino[4,3-b]indole Framework of the Uleine and Strychnos
 Alkaloids
;
_journal_name_full               'Journal of Organic Chemistry'
_journal_page_first              10773
_journal_page_last               10781
_journal_paper_doi               10.1021/jo302132d
_journal_volume                  77
_journal_year                    2012
_chemical_compound_source        local
_chemical_formula_moiety         'C15 H12 N2 O3'
_chemical_formula_sum            'C15 H12 N2 O3'
_chemical_formula_weight         268.27
_space_group_IT_number           15
_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_Hall  '-C 2yc'
_symmetry_space_group_name_H-M   'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             12-05-23
_audit_creation_method           CRYSTALS_ver_14.11
_audit_update_record
;
2012-05-23 - Report on C15 H12 N2 O3
             by Anthony C. Willis
             for  Tristan Reekie and Martin Banwell

2012-05-25 - passes checkcif tests with minor warnings  

;
_cell_angle_alpha                90
_cell_angle_beta                 97.5888(8)
_cell_angle_gamma                90
_cell_formula_units_Z            16
_cell_length_a                   40.6397(6)
_cell_length_b                   7.7179(1)
_cell_length_c                   17.0144(2)
_cell_measurement_reflns_used    34367
_cell_measurement_temperature    200
_cell_measurement_theta_max      27.5
_cell_measurement_theta_min      2.6
_cell_volume                     5289.88(12)
_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 0.997
_diffrn_measured_fraction_theta_max 0.997
_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  0.049
_diffrn_reflns_limit_h_max       52
_diffrn_reflns_limit_h_min       -52
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            54944
_diffrn_reflns_theta_full        27.522
_diffrn_reflns_theta_max         27.522
_diffrn_reflns_theta_min         2.687
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.096
_exptl_absorpt_correction_T_max  0.994
_exptl_absorpt_correction_T_min  0.968
_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    1.347
_exptl_crystal_description       plate
_exptl_crystal_F_000             2240
_exptl_crystal_size_max          0.540
_exptl_crystal_size_mid          0.190
_exptl_crystal_size_min          0.060
_refine_diff_density_max         0.33
_refine_diff_density_min         -0.28
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.9898
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     399
_refine_ls_number_reflns         6064
_refine_ls_number_restraints     20
_refine_ls_R_factor_all          0.0648
_refine_ls_R_factor_gt           0.0445
_refine_ls_shift/su_max          0.0020091
_refine_ls_shift/su_mean         0.0004274
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
;
 Method= Modified Sheldrick 
 w=1/[\s^2^(F^2^) + ( 0.05P)^2^ + 3.45P] 
 ,where P=(max(Fo^2^,0) + 2Fc^2^)/3 
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_all         0.1107
_refine_ls_wR_factor_gt          0.1016
_refine_ls_wR_factor_ref         0.1107
_reflns_limit_h_max              52
_reflns_limit_h_min              -52
_reflns_limit_k_max              10
_reflns_limit_k_min              0
_reflns_limit_l_max              22
_reflns_limit_l_min              0
_reflns_number_gt                4539
_reflns_number_total             6064
_reflns_threshold_expression     I>2.0\s(I)
_oxford_diffrn_Wilson_B_factor   3.22
_oxford_diffrn_Wilson_scale      13.80
_oxford_refine_ls_r_factor_ref   0.0648
_oxford_refine_ls_scale          0.2981(3)
_oxford_reflns_number_all        6064
_oxford_reflns_threshold_expression_ref I>-10.0\s(I)
_oxford_structure_analysis_title '5221433 ban1215'
_cod_data_source_file            jo302132d_si_002.cif
_cod_data_source_block           ban1215
_cod_original_sg_symbol_H-M      'C 1 2/c 1 '
_cod_database_code               4027772
_iucr_refine_instruction_details_constraints
;
BLOCK SCALE X'S, C(1,U'S) UNTIL O(40) 
CONT C(5,OCC) C(6,OCC) C(25,OCC) C(26,OCC) 
CONT C(51,U'S,OCC) UNTIL C(261) 
EQUIV C(5,OCC) UNTIL C(6) C(51,OCC) UNTIL C(61) 
WEIGHT -1 C(51,OCC) UNTIL C(61) 
EQUIV C(25,OCC) UNTIL C(26) C(251,OCC) UNTIL C(261) 
WEIGHT -1 C(251,OCC) UNTIL C(261) 
RIDE C   (   3,X'S) H   (  31,X'S) 
RIDE C   (   4,X'S) H(41,X'S) H(42,X'S) H(43,X'S) H(44,X'S) 
RIDE C   (   5,X'S) H   (  51,X'S) 
RIDE C   (   6,X'S) H   (  61,X'S) H   (  62,X'S) 
RIDE C   (  10,X'S) H   ( 101,X'S) H   ( 102,X'S) 
RIDE C   (  13,X'S) H   ( 131,X'S) 
RIDE C   (  14,X'S) H   ( 141,X'S) 
RIDE C   (  15,X'S) H   ( 151,X'S) 
RIDE C   (  16,X'S) H   ( 161,X'S) 
RIDE C   (  23,X'S) H   ( 231,X'S) 
RIDE C   (  24,X'S) H(241,X'S) H(242,X'S) H(243,X'S) H(244,X'S) 
RIDE C   (  25,X'S) H   ( 251,X'S) 
RIDE C   (  26,X'S) H   ( 261,X'S) H   ( 262,X'S) 
RIDE C   (  30,X'S) H   ( 301,X'S) H   ( 302,X'S) 
RIDE C   (  33,X'S) H   ( 331,X'S) 
RIDE C   (  34,X'S) H   ( 341,X'S) 
RIDE C   (  35,X'S) H   ( 351,X'S) 
RIDE C   (  36,X'S) H   ( 361,X'S) 
RIDE C(51,X'S) H(511,X'S) 
RIDE C(61,X'S) H(611,X'S) H(612,X'S) 
RIDE C(251,X'S) H(2511,X'S) 
RIDE C(261,X'S) H(2611,X'S) H(2612,X'S) 
END                                                                             
;
_iucr_refine_instruction_details_restraints
;
DIST 1.51, .02 = C(4) TO C(51) 
DIST 1.52, .02 = C(51) TO C(7) 
DIST 1.53, .02 = C(51) TO C(61) 
DIST 1.51, .02 = C(1) TO C(61) 
REM 
DIST 1.51, .02 = C(24) TO C(251) 
DIST 1.52, .02 = C(251) TO C(27) 
DIST 1.53, .02 = C(251) TO C(261) 
DIST 1.51, .02 = C(21) TO C(261) 
REM 
VIBR 0.0, .02 = C(4) TO C(51), C(51) TO C(7), C(51) TO C(61) 
CONT C(61) TO C(1) 
VIBR 0.0, .02 =  C(51) TO C(5), C(61) TO C(6) 
VIBR 0.0, .02 = C(24) TO C(251), C(251) TO C(27), C(251) TO C(261) 
CONT C(261) TO C(21) 
VIBR 0.0, .02 =  C(251) TO C(25), C(261) TO C(26) 
NO 
REM   HREST   START (DO NOT REMOVE THIS LINE) 
REM   HREST   END (DO NOT REMOVE THIS LINE) 
END                                                                             
;