The Inverse Demand Oxa-Diels-Alder Reaction of Resorcinarenes: An Experimental and Theoretical Analysis of Regioselectivity and Diastereoselectivity.
Stefańska, Karolina; Jędrzejewska, Hanna; Wierzbicki, Michał; Szumna, Agnieszka; Iwanek, Waldemar; The Journal of organic chemistry 81 (2016) 6018–6025; doi:10.1021/acs.joc.6b01099

data_4036971
_publ_section_title
;
 The Inverse Demand Oxa-Diels-Alder Reaction of Resorcinarenes: An
 Experimental and Theoretical Analysis of Regioselectivity and
 Diastereoselectivity.
;
_journal_issue                   14
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              6018
_journal_page_last               6025
_journal_paper_doi               10.1021/acs.joc.6b01099
_journal_volume                  81
_journal_year                    2016
_chemical_formula_moiety         'C84 H88 O8, 2(C7 H8)'
_chemical_formula_sum            'C98 H104 O8'
_chemical_formula_weight         1409.81
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2016-06-07
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                77.808(3)
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_cell_angle_gamma                68.049(3)
_cell_formula_units_Z            2
_cell_length_a                   14.2464(4)
_cell_length_b                   15.6824(6)
_cell_length_c                   21.1893(6)
_cell_measurement_reflns_used    16171
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      70.0766
_cell_measurement_theta_min      3.3543
_cell_volume                     4276.0(3)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.19 (release 27-10-2011 CrysAlis171 .NET)
(compiled Oct 27 2011,15:02:11)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.19 (release 27-10-2011 CrysAlis171 .NET)
(compiled Oct 27 2011,15:02:11)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.19 (release 27-10-2011 CrysAlis171 .NET)
(compiled Oct 27 2011,15:02:11)
;
_computing_molecular_graphics    'UCSF Chimera (Pettersen et al., 2004)'
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;
  1 omega  -35.00   37.00   0.9000    1.4000
omega____ theta____ kappa____ phi______ frames
    -      -33.5000   37.0000   96.0000 80

  2 omega  -87.00   11.10   0.9000    1.4000
omega____ theta____ kappa____ phi______ frames
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  3 omega  -55.00   15.20   0.9000    1.4000
omega____ theta____ kappa____ phi______ frames
    -      -33.5000   57.0000  -90.0000 78

  4 omega   39.00  121.80   0.9000    1.4000
omega____ theta____ kappa____ phi______ frames
    -       54.0000   57.0000 -180.0000 92

  5 omega   54.00  126.00   0.9000    1.4000
omega____ theta____ kappa____ phi______ frames
    -       54.0000   37.0000   90.0000 80

  6 omega   73.00  103.60   0.9000    1.4000
omega____ theta____ kappa____ phi______ frames
    -       54.0000   77.0000 -150.0000 34

  7 omega   24.00  111.30   0.9000    1.4000
omega____ theta____ kappa____ phi______ frames
    -       54.0000 -125.0000  150.0000 97

  8 omega  -12.00   68.10   0.9000    1.4000
omega____ theta____ kappa____ phi______ frames
    -       54.0000  -57.0000  -30.0000 89

  9 omega   31.00   71.50   0.9000    1.4000
omega____ theta____ kappa____ phi______ frames
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 10 omega   99.00  122.40   0.9000    1.4000
omega____ theta____ kappa____ phi______ frames
    -       54.0000   57.0000  -60.0000 26

 11 omega  -14.00   48.10   0.9000    1.4000
omega____ theta____ kappa____ phi______ frames
    -       54.0000  -77.0000  -60.0000 69

 12 omega   38.00   94.70   0.9000   28.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -25.0000 -120.0000 63

 13 omega   44.00  114.20   0.9000   28.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000 -111.0000  -60.0000 78

 14 omega   62.00   89.00   0.9000   28.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -25.0000 -180.0000 30

 15 omega  121.00  177.70   0.9000   28.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   25.0000   30.0000 63

 16 omega   39.00   92.10   0.9000   28.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -37.0000    0.0000 59

 17 omega   61.00  114.10   0.9000   28.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000 -111.0000  150.0000 59

 18 omega   44.00   91.70   0.9000   28.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -77.0000  -60.0000 53

 19 omega   39.00   74.10   0.9000   28.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -37.0000   60.0000 39

 20 omega   64.00   91.00   0.9000   28.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -25.0000   90.0000 30

 21 omega   40.00   84.10   0.9000   28.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -37.0000  150.0000 49

 22 omega   35.00   90.80   0.9000   28.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -25.0000  -60.0000 62

 23 omega   41.00   66.20   0.9000   28.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000 -111.0000   30.0000 28

 24 omega   78.00  113.10   0.9000   28.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000 -111.0000   30.0000 39

 25 omega   86.00  129.20   0.9000   28.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -77.0000    0.0000 48

 26 omega   50.00   90.50   0.9000   28.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -50.0000   90.0000 45

 27 omega   55.00   82.00   0.9000   28.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -37.0000 -180.0000 30

 28 omega   62.00  108.80   0.9000   28.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -91.0000 -150.0000 52

 29 omega   51.00   82.50   0.9000   28.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -77.0000    0.0000 35

 30 omega   36.00   65.70   0.9000   28.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -37.0000 -120.0000 33

 31 omega  111.00  138.00   0.9000   28.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -77.0000  -60.0000 30

 32 omega   45.00  178.20   0.9000   28.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -12.0000    0.0000 148

 33 omega   60.00  120.30   0.9000   28.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -77.0000  150.0000 67
;
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0990045000
_diffrn_orient_matrix_UB_12      -0.0153215000
_diffrn_orient_matrix_UB_13      -0.0336836000
_diffrn_orient_matrix_UB_21      0.0010416000
_diffrn_orient_matrix_UB_22      -0.0942368000
_diffrn_orient_matrix_UB_23      -0.0112424000
_diffrn_orient_matrix_UB_31      -0.0623780000
_diffrn_orient_matrix_UB_32      0.0520880000
_diffrn_orient_matrix_UB_33      -0.0656725000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0299
_diffrn_reflns_av_unetI/netI     0.0380
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.975
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            32476
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.975
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         70.208
_diffrn_reflns_theta_min         3.357
_diffrn_source                   'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.529
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.68517
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
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CrysAlisPro, Agilent Technologies,
Version 1.171.35.19 (release 27-10-2011 CrysAlis171 .NET)
(compiled Oct 27 2011,15:02:11)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
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_exptl_crystal_description       prism
_exptl_crystal_F_000             1512
_refine_diff_density_max         0.678
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_refine_ls_extinction_method     none
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_refine_ls_hydrogen_treatment    constr
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_refine_ls_number_parameters     1022
_refine_ls_number_reflns         15903
_refine_ls_number_restraints     15
_refine_ls_restrained_S_all      1.049
_refine_ls_R_factor_all          0.0707
_refine_ls_R_factor_gt           0.0616
_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^)+(0.0883P)^2^+2.5687P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
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_refine_ls_wR_factor_ref         0.1766
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13198
_reflns_number_total             15903
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo6b01099_si_003.cif
_cod_data_source_block           ome_indene
_cod_database_code               4036971
_shelxl_version_number           2013-4
_reflns_odcompleteness_completeness 99.95
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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, All O(H) groups
2. Rigid bond restraints
 C4, C14, C11, C6, C1, C2, C9
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.01
3. Others
 Sof(C4)=Sof(H4A)=Sof(H4B)=Sof(H4C)=Sof(C9)=Sof(H9)=Sof(C14)=Sof(C11)=Sof(H11)=
 Sof(C6)=Sof(H6)=Sof(C1)=Sof(H1)=Sof(C2)=Sof(H2)=1-FVAR(1)
 Sof(C02M)=Sof(H9AA)=Sof(C02O)=Sof(H0BA)=Sof(C02Q)=Sof(C02R)=Sof(H1BA)=
 Sof(C02T)=Sof(H2BA)=Sof(C02V)=Sof(H3BA)=Sof(C02Z)=Sof(H4BA)=Sof(HC)=Sof(HD)=
 FVAR(1)
4.a Ternary CH refined with riding coordinates:
 C00K(H00K), C00O(H00O), C00R(H00R), C010(H010), C011(H011), C013(H013),
 C014(H014), C017(H017), C01E(H01F), C01F(H01G), C01G(H01H), C01H(H01I),
 C01L(H01N), C01O(H01R), C01W(H0AA), C01Y(H2AA)
4.b Secondary CH2 refined with riding coordinates:
 C00J(H00A,H00C), C00T(H00D,H00F), C00X(H00H,H00I), C00Y(H00J,H00L), C01A(H01A,
 H01B), C01B(H01C,H01D), C01I(H01J,H01K), C01K(H01L,H01M), C01U(H01,H),
 C02B(H02J,H02K), C02C(H02L,H02M), C02G(H02U,H02V)
4.c Aromatic/amide H refined with riding coordinates:
 C00B(H00B), C00E(H00E), C00G(H00G), C01C(H01E), C01P(H01S), C01S(H01Z),
 C01X(H1AA), C01Z(H3AA), C021(H021), C022(H022), C023(H023), C025(H025),
 C027(H027), C028(H028), C029(H029), C02E(H02Q), C02H(H02W), C02I(H02X),
 C02J(H02Y), C02K(H02Z), C02L(H02), C02M(H9AA), C02O(H0BA), C02P(H4AA),
 C02R(H1BA), C02T(H2BA), C02U(H6AA), C02V(H3BA), C02W(H7AA), C02X(H8AA), C9(H9),
  C11(H11), C6(H6), C1(H1), C2(H2)
4.d Fitted hexagon refined as free rotating group:
 C9(C14,C11,C6,C1,C2)
4.e Idealised Me refined as rotating group:
 C01N(H01O,H01P,H01Q), C01Q(H01T,H01U,H01V), C01R(H01W,H01X,H01Y), C020(H02A,
 H02B,H02C), C024(H02D,H02E,H02F), C02A(H02G,H02H,H02I), C02D(H02N,H02O,H02P),
 C02F(H02R,H02S,H02T), C02S(H5AA,HA,HB), C02Z(H4BA,HC,HD), C4(H4A,H4B,H4C)
4.f Idealised tetrahedral OH refined as rotating group:
 O001(H001), O005(H005), O007(H007), O008(H008)
;
_shelx_res_checksum              36639
_shelx_hkl_checksum              64878
_olex2_submission_special_instructions 'No special instructions were received'