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_4031065
_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 rmad
_chemical_formula_moiety         'C24 H23 I N2 O5, 0.5(C3 H6 O)'
_chemical_formula_sum            'C25.5 H26 I N2 O5.5'
_chemical_formula_weight         575.38
_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   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2014-09-22
_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            8
_cell_length_a                   5.2638(2)
_cell_length_b                   19.7530(8)
_cell_length_c                   46.4372(18)
_cell_measurement_reflns_used    9295
_cell_measurement_temperature    150
_cell_measurement_theta_max      70.004
_cell_measurement_theta_min      2.431
_cell_volume                     4828.3(3)
_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      150
_diffrn_detector                 'CCD area detector'
_diffrn_detector_area_resol_mean 8.3
_diffrn_detector_type            'Bruker Platinum 135 CCD Area Detector'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device       'k-geometry diffractometer'
_diffrn_measurement_device_type  'Bruker Microstar X8'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_collimation    'Focusing mirrors'
_diffrn_radiation_monochromator  'Helios Mirror Optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0737
_diffrn_reflns_av_unetI/netI     0.0441
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -5
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       56
_diffrn_reflns_limit_l_min       -56
_diffrn_reflns_number            90175
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         70.630
_diffrn_reflns_theta_min         1.903
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_target            Cu
_diffrn_source_type              'Bruker Microstar/FR591 generator'
_exptl_absorpt_coefficient_mu    10.774
_exptl_absorpt_correction_T_max  0.7534
_exptl_absorpt_correction_T_min  0.5102
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/2 (Bruker,2014) was used for absorption correction.
wR2(int) was 0.1423 before and 0.0990 after correction.
The Ratio of minimum to maximum transmission is 0.6772.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            Colorless
_exptl_crystal_density_diffrn    1.583
_exptl_crystal_description       block
_exptl_crystal_F_000             2320
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.03
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.660
_refine_diff_density_min         -0.460
_refine_diff_density_rms         0.067
_refine_ls_abs_structure_details
;
 Flack x determined using 3295 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.020(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.047
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     620
_refine_ls_number_reflns         9214
_refine_ls_number_restraints     14
_refine_ls_restrained_S_all      1.050
_refine_ls_R_factor_all          0.0347
_refine_ls_R_factor_gt           0.0301
_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^)+(0.0385P)^2^+0.2429P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0734
_refine_ls_wR_factor_ref         0.0752
_reflns_Friedel_coverage         0.726
_reflns_Friedel_fraction_full    0.998
_reflns_Friedel_fraction_max     0.990
_reflns_number_gt                8442
_reflns_number_total             9214
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo5b00237_si_003.cif
_cod_data_source_block           lube80
_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 

2025-10-08
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_formula_sum            'C51 H52 I2 N4 O11'
_cod_original_formula_weight         1150.76
_cod_original_formula_moiety         '2(C24 H23 I N2 O5), C3 H6 O'
_cod_original_formula_units_Z            4
_cod_database_code               4031065
_shelxl_version_number           2014-3
_shelx_estimated_absorpt_t_max   0.813
_shelx_estimated_absorpt_t_min   0.222
_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. Restrained distances
 O61B-C61B \\sim O61A-C61A
 with sigma of 0.01
 C61B-C62B \\sim C61B-C63B \\sim C61A-C62A \\sim C61A-C63A
 with sigma of 0.01
 O61B-C62B \\sim O61B-C63B \\sim O61A-C62A \\sim O61A-C63A
 with sigma of 0.04
 C63B-C62B \\sim C63A-C62A
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
: with sigma of 0.04 and sigma for terminal atoms of 0.08
Uiso(O61A) = Uiso(O61B)
Uiso(C61A) = Uiso(C61B)
Uiso(C62A) = Uiso(C62B)
Uiso(C63A) = Uiso(C63B)
4. Others
 Sof(O61B)=Sof(C61B)=Sof(C62B)=Sof(H62D)=Sof(H62E)=Sof(H62F)=Sof(C63B)=
 Sof(H63D)=Sof(H63E)=Sof(H63F)=1-FVAR(1)
 Sof(O61A)=Sof(C61A)=Sof(C62A)=Sof(H62A)=Sof(H62B)=Sof(H62C)=Sof(C63A)=
 Sof(H63A)=Sof(H63B)=Sof(H63C)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C2(H2A), C3(H3), C4(H4), C7(H7), C12(H12), C32(H32A), C33(H33), C34(H34),
 C37(H37), C42(H42)
5.b Secondary CH2 refined with riding coordinates:
 C5(H5A,H5B), C6(H6A,H6B), C11(H11A,H11B), C35(H35A,H35B), C36(H36A,H36B),
 C41(H41A,H41B)
5.c Aromatic/amide H refined with riding coordinates:
 C14(H14), C15(H15), C16(H16), C17(H17), C20(H20), C21(H21), C22(H22),
 C23(H23), C44(H44), C45(H45), C46(H46), C47(H47), C50(H50), C51(H51), C52(H52),
  C53(H53)
5.d Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C), C39(H39A,H39B,H39C), C62A(H62A,H62B,H62C), C63A(H63A,H63B,
 H63C), C62B(H62D,H62E,H62F), C63B(H63D,H63E,H63F)
;
_olex2_submission_special_instructions 'No special instructions were received'