Insight into Transannular Cyclization Reactions To Synthesize Azabicyclo[X.Y.Z]alkanone Amino Acid Derivatives from 8-, 9-, and 10-Membered Macrocyclic Dipeptide Lactams.
Atmuri, N. D. Prasad; Lubell, William D.; The Journal of organic chemistry 80 (2015) 4904–4918; doi:10.1021/acs.joc.5b00237

data_4031069
_publ_section_title
;
 Insight into Transannular Cyclization Reactions To Synthesize
 Azabicyclo[X.Y.Z]alkanone Amino Acid Derivatives from 8-, 9-, and
 10-Membered Macrocyclic Dipeptide Lactams.
;
_journal_issue                   10
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              4904
_journal_page_last               4918
_journal_paper_doi               10.1021/acs.joc.5b00237
_journal_volume                  80
_journal_year                    2015
_chemical_absolute_configuration rm
_chemical_formula_moiety         'C35 H38 N2 O7'
_chemical_formula_sum            'C35 H38 N2 O7'
_chemical_formula_weight         598.67
_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'
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2014-11-13
_audit_creation_method
;
Olex2 1.2
(compiled 2014.09.19 svn.r3010 for OlexSys, GUI svn.r4874)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.4075(8)
_cell_length_b                   12.1987(10)
_cell_length_c                   27.339(2)
_cell_measurement_reflns_used    7161
_cell_measurement_temperature    100
_cell_measurement_theta_max      48.294
_cell_measurement_theta_min      2.813
_cell_volume                     3137.4(4)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_collection
;
APEX 2 (2013) Bruker AXS Inc., Madison, WI 53719-1173.
;
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_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    'XT (Sheldrick, 2008)'
_diffrn_ambient_temperature      100
_diffrn_detector                 'CMOS Area detector'
_diffrn_detector_area_resol_mean 10.24
_diffrn_detector_type            'Bruker Photon 100 CMOS Detector'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.988
_diffrn_measurement_device       'k-geometry diffractometer'
_diffrn_measurement_device_type  'Bruker Venture Metaljet'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_collimation    'Focusing mirrors'
_diffrn_radiation_monochromator  'Helios MX Mirror Optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           GaK\a
_diffrn_radiation_wavelength     1.34139
_diffrn_reflns_av_R_equivalents  0.0988
_diffrn_reflns_av_unetI/netI     0.0916
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       35
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            28548
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.972
_diffrn_reflns_theta_full        53.594
_diffrn_reflns_theta_max         60.760
_diffrn_reflns_theta_min         2.812
_diffrn_source                   'Metal Jet'
_diffrn_source_target            Ga
_diffrn_source_type              'Gallium Liquid Metal Jet Source'
_exptl_absorpt_coefficient_mu    0.462
_exptl_absorpt_correction_T_max  0.7519
_exptl_absorpt_correction_T_min  0.5052
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/4 (Bruker,2014) was used for absorption correction.
wR2(int) was 0.1243 before and 0.0847 after correction.
The Ratio of minimum to maximum transmission is 0.6719.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.267
_exptl_crystal_description       block
_exptl_crystal_F_000             1272
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.223
_refine_diff_density_min         -0.177
_refine_diff_density_rms         0.042
_refine_ls_abs_structure_details
;
 Flack x determined using 1396 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.3(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.012
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     413
_refine_ls_number_reflns         7022
_refine_ls_number_restraints     69
_refine_ls_restrained_S_all      1.009
_refine_ls_R_factor_all          0.1170
_refine_ls_R_factor_gt           0.0547
_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^)+(0.0445P)^2^+0.2877P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1057
_refine_ls_wR_factor_ref         0.1246
_reflns_Friedel_coverage         0.749
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.952
_reflns_number_gt                4157
_reflns_number_total             7022
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo5b00237_si_007.cif
_cod_data_source_block           lube87
_cod_depositor_comments
;
The following automatic conversions were performed:

'_diffrn_radiation_probe' value 'X-ray' changed to 'x-ray' according
to
/usr/data/users/saulius/crontab/automatic-downloads/current/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 3271 2015-04-21 07:52:19Z andrius 
;
_cod_original_cell_volume        3137.4(5)
_cod_database_code               4031069
_shelxl_version_number           2014/6
_shelx_estimated_absorpt_t_max   0.991
_shelx_estimated_absorpt_t_min   0.947
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups, All N(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 N1-C21A \\sim N1-C21B
 with sigma of 0.02
 C12-C13A \\sim C12-C13B
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C13A) = Uanis(C13B)
Uanis(C14A) = Uanis(C14B)
Uanis(C15A) = Uanis(C15B)
Uanis(C16A) = Uanis(C16B)
Uanis(C17A) = Uanis(C17B)
Uanis(C18A) = Uanis(C18B)
Uanis(C19A) = Uanis(C19B)
Uanis(C20A) = Uanis(C20B)
Uanis(C21A) = Uanis(C21B)
Uanis(O4A) = Uanis(O4B)
Uanis(O5A) = Uanis(O5B)
Uanis(O6A) = Uanis(O6B)
Uanis(O7A) = Uanis(O7B)
Uanis(C22A) = Uanis(C22B)
Uanis(C23A) = Uanis(C23B)
Uanis(C24A) = Uanis(C24B)
Uanis(C25A) = Uanis(C25B)
Uanis(C26A) = Uanis(C26B)
Uanis(C27A) = Uanis(C27B)
Uanis(C28A) = Uanis(C28B)
Uanis(C29A) = Uanis(C29B)
Uanis(C35A) = Uanis(C35B)
Uanis(C34A) = Uanis(C34B)
Uanis(C30A) = Uanis(C30B)
Uanis(C31A) = Uanis(C31B)
Uanis(C32A) = Uanis(C32B)
Uanis(C33A) = Uanis(C33B)
Uanis(C34A) = Uanis(C34B)
Uanis(C35A) = Uanis(C35B)
4. Same fragment restrains
{C13A, C14A, C15A, C16A, C17A, C18A, O4A, C19A, O5A, C20A}
as
{C13B, C14B, C15B, C16B, C17B, C18B, O4B, C19B, O5B, C20B}
{O6A, O7A, C21A, C22A, C23A, C24A, C25A, C26A, C27A, C28A, C29A, C30A, C31A,
C32A, C33A, C34A, C35A}
as
{O6B, O7B, C21B, C22B, C23B, C24B, C25B, C26B, C27B, C28B, C29B, C30B, C31B,
C32B, C33B, C34B, C35B}
5. Others
 Sof(H12C)=Sof(H12D)=Sof(C13B)=Sof(C14B)=Sof(C15B)=Sof(H15B)=Sof(C16B)=
 Sof(C17B)=Sof(H17B)=Sof(C18B)=Sof(H18B)=Sof(O4B)=Sof(C19B)=Sof(H19D)=Sof(H19E)=
 Sof(H19F)=Sof(O5B)=Sof(C20B)=Sof(H20D)=Sof(H20E)=Sof(H20F)=1-FVAR(1)
 Sof(H12A)=Sof(H12B)=Sof(C13A)=Sof(C14A)=Sof(C15A)=Sof(H15A)=Sof(C16A)=
 Sof(C17A)=Sof(H17A)=Sof(C18A)=Sof(H18A)=Sof(O4A)=Sof(C19A)=Sof(H19A)=Sof(H19B)=
 Sof(H19C)=Sof(O5A)=Sof(C20A)=Sof(H20A)=Sof(H20B)=Sof(H20C)=FVAR(1)
 Sof(H1)=Sof(O6B)=Sof(O7B)=Sof(C21B)=Sof(C22B)=Sof(H22C)=Sof(H22D)=Sof(C23B)=
 Sof(H23B)=Sof(C24B)=Sof(C25B)=Sof(H25B)=Sof(C26B)=Sof(H26B)=Sof(C27B)=
 Sof(H27B)=Sof(C28B)=Sof(H28B)=Sof(C29B)=Sof(C30B)=Sof(C31B)=Sof(H31B)=
 Sof(C32B)=Sof(H32B)=Sof(C33B)=Sof(H33B)=Sof(C34B)=Sof(H34B)=Sof(C35B)=1-FVAR(2)
 Sof(H1A)=Sof(O6A)=Sof(O7A)=Sof(C21A)=Sof(C22A)=Sof(H22A)=Sof(H22B)=Sof(C23A)=
 Sof(H23A)=Sof(C24A)=Sof(C25A)=Sof(H25A)=Sof(C26A)=Sof(H26A)=Sof(C27A)=
 Sof(H27A)=Sof(C28A)=Sof(H28A)=Sof(C29A)=Sof(C30A)=Sof(C31A)=Sof(H31A)=
 Sof(C32A)=Sof(H32A)=Sof(C33A)=Sof(H33A)=Sof(C34A)=Sof(H34A)=Sof(C35A)=FVAR(2)
6.a Ternary CH refined with riding coordinates:
 C1(H1B), C3(H3), C23A(H23A), C23B(H23B)
6.b Secondary CH2 refined with riding coordinates:
 C4(H4A,H4B), C5(H5A,H5B), C6(H6A,H6B), C9(H9A,H9B), C12(H12A,H12B), C12(H12C,
 H12D), C22A(H22A,H22B), C22B(H22C,H22D)
6.c Aromatic/amide H refined with riding coordinates:
 N1(H1A), N1(H1), C7(H7), C8(H8), C15A(H15A), C17A(H17A), C18A(H18A),
 C15B(H15B), C17B(H17B), C18B(H18B), C25A(H25A), C26A(H26A), C27A(H27A),
 C28A(H28A), C31A(H31A), C32A(H32A), C33A(H33A), C34A(H34A), C25B(H25B),
 C26B(H26B), C27B(H27B), C28B(H28B), C31B(H31B), C32B(H32B), C33B(H33B),
 C34B(H34B)
6.d Fitted hexagon refined as free rotating group:
 C13A(C14A,C15A,C16A,C17A,C18A), C13B(C14B,C15B,C16B,C17B,C18B), C24A(C25A,
 C26A,C27A,C28A,C29A), C30A(C31A,C32A,C33A,C34A,C35A), C24B(C25B,C26B,C27B,C28B,
 C29B), C30B(C31B,C32B,C33B,C34B,C35B)
6.e Idealised Me refined as rotating group:
 C11(H11A,H11B,H11C), C19A(H19A,H19B,H19C), C20A(H20A,H20B,H20C), C19B(H19D,
 H19E,H19F), C20B(H20D,H20E,H20F)
;
_olex2_submission_special_instructions 'No special instructions were received'