Formal [3+2] Cycloaddition of Nitrosoallenes with Carbonyl and Nitrile Compounds to Form Functional Cyclic Nitrones.
Tanimoto, Hiroki; Shitaoka, Takashi; Yokoyama, Keiichi; Morimoto, Tsumoru; Nishiyama, Yasuhiro; Kakiuchi, Kiyomi; The Journal of organic chemistry 81 (2016) 8722–8735; doi:10.1021/acs.joc.6b00758

data_4036877
_publ_section_title
;
 Formal [3+2] Cycloaddition of Nitrosoallenes with Carbonyl and Nitrile
 Compounds to Form Functional Cyclic Nitrones.
;
_journal_issue                   19
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              8722
_journal_page_last               8735
_journal_paper_doi               10.1021/acs.joc.6b00758
_journal_volume                  81
_journal_year                    2016
_chemical_absolute_configuration 'CHOOSE rm ad rmad syn or unk'
_chemical_formula_moiety         'C25 H27 N O5'
_chemical_formula_sum            'C25 H27 N O5'
_chemical_formula_weight         421.49
_space_group_crystal_system      orthorhombic
_space_group_IT_number           29
_space_group_name_Hall           'P 2c -2ac'
_space_group_name_H-M_alt        'P c a 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_cell_angle_alpha                90.0000
_cell_angle_beta                 90.0000
_cell_angle_gamma                90.0000
_cell_formula_units_Z            4
_cell_length_a                   22.5932(4)
_cell_length_b                   9.89595(19)
_cell_length_c                   9.79336(18)
_cell_measurement_reflns_used    31330
_cell_measurement_temperature    123
_cell_measurement_theta_max      27.51
_cell_measurement_theta_min      3.06
_cell_volume                     2189.61(7)
_computing_cell_refinement       'RAPID AUTO'
_computing_data_collection       'RAPID AUTO (Rigaku, ????)'
_computing_data_reduction        'RAPID AUTO'
_computing_molecular_graphics    'CrystalStructure 4.1'
_computing_publication_material  'CrystalStructure 4.1 (Rigaku, 2014)'
_computing_structure_refinement  'SHELXL2013 (Sheldrick, 2008)'
_computing_structure_solution    'SIR2011 (Burla, et al., 2012)'
_diffrn_ambient_temperature      123
_diffrn_detector_area_resol_mean 10.000
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Rigaku R-AXIS RAPID'
_diffrn_measurement_method       \w
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71075
_diffrn_reflns_av_R_equivalents  0.0294
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       29
_diffrn_reflns_limit_h_min       -29
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            36450
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.989
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.484
_diffrn_reflns_theta_min         3.062
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.089
_exptl_absorpt_correction_T_max  0.996
_exptl_absorpt_correction_T_min  0.842
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'ABSCOR (Rigaku, 1995)'
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.278
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       prism
_exptl_crystal_F_000             896.00
_exptl_crystal_size_max          0.150
_exptl_crystal_size_mid          0.100
_exptl_crystal_size_min          0.050
_refine_diff_density_max         0.32
_refine_diff_density_min         -0.19
_refine_ls_abs_structure_details
;
 Flack x determined using 2036 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   0.01(16)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.076
_refine_ls_hydrogen_treatment    constr
_refine_ls_number_parameters     283
_refine_ls_number_reflns         4959
_refine_ls_number_restraints     1
_refine_ls_R_factor_all          0.0323
_refine_ls_R_factor_gt           0.0295
_refine_ls_shift/su_max          0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w = 1/[\s^2^(Fo^2^)+(0.0398P)^2^+0.4038P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0721
_refine_ls_wR_factor_ref         0.0737
_reflns_number_gt                4677
_reflns_number_total             4959
_reflns_threshold_expression     F^2^>2.0\s(F^2^)
_cod_data_source_file            jo6b00758_si_002.cif
_cod_data_source_block           TS_02_103
_cod_database_code               4036877
_shelxl_res_file
;
TITL TS_02_103
CELL  0.71075 22.59316 9.89595 9.79336 90.00000 90.00000 90.00000
ZERR  4 0.00042 0.00019 0.00018 0.00000 0.00000 0.00000
LATT -1
SYMM .50-X,    +Y, .50+Z
SYMM .50+X,    -Y,    +Z
SYMM    -X,    -Y, .50+Z
SFAC C H N O
UNIT 100 108 4 20
L.S. 5
FMAP 2
PLAN -20
WPDB -2
HTAB
BOND $H
CONF
LIST 4
TEMP -150.0
ACTA
SIZE 0.150 0.100 0.050
WGHT    0.039800    0.403800
FVAR       0.69659
O1    4    0.785007    0.640311    0.511796    11.00000    0.01988    0.02458 =
         0.02565   -0.00006   -0.00751   -0.00676
O2    4    0.905104    0.732477    0.881134    11.00000    0.02238    0.02165 =
         0.01334    0.00217   -0.00127    0.00042
O3    4    0.878367    0.793085    0.407848    11.00000    0.01560    0.02148 =
         0.01104    0.00142   -0.00031    0.00383
O4    4    0.785898    0.876593    0.322428    11.00000    0.01246    0.02830 =
         0.01493    0.00189   -0.00118    0.00148
O5    4    0.719355    0.961838    0.461458    11.00000    0.01535    0.03176 =
         0.02546    0.00745    0.00147    0.00609
N1    3    0.824106    0.689333    0.589460    11.00000    0.01203    0.01536 =
         0.01917   -0.00009   -0.00035   -0.00093
C1    1    0.859814    0.812781    0.540443    11.00000    0.01294    0.01462 =
         0.01283   -0.00012    0.00084    0.00016
C2    1    0.835708    0.655608    0.716413    11.00000    0.01473    0.01614 =
         0.01827    0.00053    0.00236    0.00190
C3    1    0.885451    0.735159    0.765750    11.00000    0.01479    0.01393 =
         0.01504    0.00092    0.00257    0.00299
C4    1    0.912343    0.812594    0.643621    11.00000    0.01238    0.01437 =
         0.01319    0.00100   -0.00009    0.00034
C5    1    0.847850    0.852015    0.292976    11.00000    0.01323    0.02189 =
         0.01349    0.00224   -0.00054    0.00184
C6    1    0.769508    0.926060    0.444910    11.00000    0.01680    0.01767 =
         0.01843    0.00513    0.00095    0.00102
C7    1    0.817294    0.932867    0.552922    11.00000    0.01381    0.01688 =
         0.01564   -0.00015    0.00093    0.00304
AFIX  23
H7A   2    0.798828    0.932444    0.644595    11.00000   -1.20000
H7B   2    0.839707    1.018248    0.542819    11.00000   -1.20000
AFIX   0
C8    1    0.877260    0.983472    0.251684    11.00000    0.01953    0.02245 =
         0.02076    0.00467    0.00342    0.00006
AFIX 137
H8A   2    0.856958    1.021038    0.171815    11.00000   -1.20000
H8B   2    0.918850    0.966469    0.229046    11.00000   -1.20000
H8C   2    0.874987    1.047905    0.327494    11.00000   -1.20000
AFIX   0
C9    1    0.849547    0.746603    0.183082    11.00000    0.02224    0.02773 =
         0.01448   -0.00256   -0.00222   -0.00065
AFIX 137
H9A   2    0.890769    0.727816    0.158403    11.00000   -1.20000
H9B   2    0.828160    0.779512    0.102625    11.00000   -1.20000
H9C   2    0.830820    0.663581    0.216389    11.00000   -1.20000
AFIX   0
C10   1    0.802599    0.550804    0.792436    11.00000    0.01687    0.01744 =
         0.02353    0.00386    0.00307   -0.00133
AFIX  23
H10A  2    0.759943    0.559542    0.771057    11.00000   -1.20000
H10B  2    0.807609    0.566668    0.891574    11.00000   -1.20000
AFIX   0
C11   1    0.822668    0.407051    0.758870    11.00000    0.02582    0.01863 =
         0.05057    0.00477    0.00779    0.00079
AFIX  23
H11A  2    0.813377    0.386907    0.662199    11.00000   -1.20000
H11B  2    0.866094    0.400474    0.770621    11.00000   -1.20000
AFIX   0
C12   1    0.792452    0.302710    0.850393    11.00000    0.03521    0.02506 =
         0.08730    0.02074    0.00838   -0.00096
AFIX  23
H12A  2    0.808734    0.212347    0.828700    11.00000   -1.20000
H12B  2    0.802552    0.322968    0.946607    11.00000   -1.20000
AFIX   0
C13   1    0.726510    0.297162    0.837308    11.00000    0.03723    0.03767 =
         0.08750    0.01169    0.00313   -0.01307
AFIX 137
H13A  2    0.709640    0.384990    0.862262    11.00000   -1.20000
H13B  2    0.710841    0.227280    0.898306    11.00000   -1.20000
H13C  2    0.715860    0.275582    0.742785    11.00000   -1.20000
AFIX   0
C14   1    0.964402    0.718889    0.603814    11.00000    0.01471    0.01462 =
         0.01377    0.00281    0.00255    0.00093
C15   1    0.959725    0.609439    0.514619    11.00000    0.02005    0.01549 =
         0.01931    0.00158   -0.00132    0.00079
AFIX  43
H15   2    0.923246    0.591852    0.469770    11.00000   -1.20000
AFIX   0
C16   1    1.008287    0.525782    0.490976    11.00000    0.02546    0.01463 =
         0.02138    0.00106    0.00448    0.00426
AFIX  43
H16   2    1.004960    0.453228    0.427920    11.00000   -1.20000
AFIX   0
C17   1    1.061297    0.547272    0.558369    11.00000    0.02047    0.02026 =
         0.02534    0.00571    0.00694    0.00788
AFIX  43
H17   2    1.094367    0.490484    0.541145    11.00000   -1.20000
AFIX   0
C18   1    1.065661    0.652637    0.651383    11.00000    0.01615    0.02402 =
         0.02558    0.00492   -0.00207    0.00198
AFIX  43
H18   2    1.101573    0.666622    0.699821    11.00000   -1.20000
AFIX   0
C19   1    1.017724    0.737767    0.673966    11.00000    0.01770    0.01905 =
         0.01756    0.00127    0.00037    0.00042
AFIX  43
H19   2    1.021198    0.809627    0.737787    11.00000   -1.20000
AFIX   0
C20   1    0.933423    0.955843    0.671868    11.00000    0.01176    0.01443 =
         0.01559    0.00063   -0.00181    0.00170
C21   1    0.919867    1.025937    0.791239    11.00000    0.01758    0.01839 =
         0.01522    0.00000   -0.00070    0.00134
AFIX  43
H21   2    0.897602    0.983246    0.861314    11.00000   -1.20000
AFIX   0
C22   1    0.939048    1.158835    0.807610    11.00000    0.02299    0.01720 =
         0.02011   -0.00348   -0.00184    0.00419
AFIX  43
H22   2    0.930492    1.205617    0.889985    11.00000   -1.20000
AFIX   0
C23   1    0.970414    1.223430    0.705245    11.00000    0.02119    0.01444 =
         0.02700   -0.00135   -0.00389   -0.00107
AFIX  43
H23   2    0.982909    1.314356    0.716956    11.00000   -1.20000
AFIX   0
C24   1    0.983569    1.154602    0.585076    11.00000    0.01804    0.01899 =
         0.02172    0.00293    0.00133   -0.00122
AFIX  43
H24   2    1.004841    1.198600    0.514189    11.00000   -1.20000
AFIX   0
C25   1    0.965494    1.021366    0.569135    11.00000    0.01584    0.01851 =
         0.01635    0.00009    0.00047    0.00057
AFIX  43
H25   2    0.975016    0.974198    0.487553    11.00000   -1.20000
AFIX   0
HKLF 4
 
REM  TS_02_103
REM R1 =  0.0295 for    4677 Fo > 4sig(Fo)  and  0.0323 for all    4959 data
REM    283 parameters refined using      1 restraints
 
END  
     
WGHT      0.0398      0.4037 

REM Instructions for potential hydrogen bonds
EQIV $1 -x+3/2, y, z+1/2
HTAB C7 O4_$1
EQIV $2 -x+3/2, y, z-1/2
HTAB C9 O5_$2
HTAB C10 O1_$1

REM Highest difference peak  0.321,  deepest hole -0.186,  1-sigma level  0.035
Q1    1   0.7740  0.2889  0.9503  11.00000  0.05    0.32
Q2    1   0.8896  0.8144  0.5913  11.00000  0.05    0.25
Q3    1   0.9212  0.8829  0.6640  11.00000  0.05    0.24
Q4    1   0.9361  0.7659  0.6255  11.00000  0.05    0.23
Q5    1   0.8999  0.7717  0.7021  11.00000  0.05    0.22
Q6    1   0.7667  0.2981  0.7721  11.00000  0.05    0.20
Q7    1   0.8400  0.8705  0.5475  11.00000  0.05    0.19
Q8    1   0.7909  0.9190  0.5052  11.00000  0.05    0.18
Q9    1   0.9467  1.0782  0.8183  11.00000  0.05    0.18
Q10   1   0.9888  0.7090  0.6486  11.00000  0.05    0.18
Q11   1   0.8624  0.9195  0.2778  11.00000  0.05    0.18
Q12   1   0.8581  0.6933  0.7419  11.00000  0.05    0.17
Q13   1   0.8072  0.4798  0.7661  11.00000  0.05    0.16
Q14   1   0.8518  0.7991  0.2399  11.00000  0.05    0.16
Q15   1   1.0568  0.5913  0.6139  11.00000  0.05    0.16
Q16   1   0.8437  0.7498  0.5640  11.00000  0.05    0.16
Q17   1   0.9828  0.5562  0.5232  11.00000  0.05    0.15
Q18   1   0.9884  0.5813  0.4959  11.00000  0.05    0.15
Q19   1   0.9301  0.9841  0.7225  11.00000  0.05    0.14
Q20   1   0.9708  1.1748  0.6432  11.00000  0.05    0.14
;