Study of Substrate Dependence on the Diastereoselectivity of the Ruthe­nium(II) Porphyrin Catalyzed Tandem Formation and 1,3-Dipolar Cyclo­addition Reactions of Carbonyl Ylides

Abstract

The effect of substrate substitution on reaction selectivity for the ruthenium(II) porphyrin catalyzed tandem carbonyl ylide formation/1,3-dipolar cycloaddition reaction of a variety of alkyl and aryl substituted α-diazo ketones 1 with π-unsaturated compounds was examined. The results suggested the diastereoselectivity of the reaction to be highly substrate dependant. Similar yields and cis/trans selectivities have also been achieved for the analogous reactions with rhodium(II,II) dimer as catalyst.

Key words

carbonyl ylide formation - 1,3-dipolar cycloaddition - metallocarbenoids - rhodium(II,II) dimers - ruthenium(II) porphyrins

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11

4-[(2,4-Dinitro-phenyl)-hydrazono]-2-ethyl-1-phenyl-8-oxa-bicyclo[3.2.1]oct-6-ene-6,7-Dicarboxylic Acid Dimethyl Ester (3) (Scheme [3] ) Yellow crystals; mp 230-232 °C.
IR (KBr): 3326, 3082, 2963, 1757, 1718, 1624, 1583, 1495, 1435, 1335, 1259, 1200, 1140, 1005 cm^-1,
¹H NMR (400 MHz, CDCl₃): δ = 11.2 (s, 1 H), 9.14 (d, 1 H, J = 2.5 Hz), 8.36 (dd, 1 H, J = 9.6, 2.5 Hz), 8.06 (d, 1H, J = 9.6 Hz), 7.32-7.42 (m, 5 H), 5.57 (s, 1 H), 3.77 (s, 3 H), 3.70 (s, 3 H), 2.90 (d, 1 H, J = 16.4 Hz), 2.84 (dd, 1 H, J = 16.4, 6.5 Hz), 2.64 (m, 1 H), 1.32-1.38 (m, 1 H), 1.20-1.28 (m, 1 H), 0.93 (t, 3 H, J = 7.4 Hz).
¹³C NMR (100 MHz, CDCl₃): δ = 164.6 (s), 161.0 (s), 149.2 (s), 149.0 (s), 145.1 (s), 138.4 (s), 136.7 (s), 133.2 (s), 130.1 (d), 129.7 (s), 128.6 (d), 128.2 (d), 124.9 (d), 123.2 (d), 116.6 (d), 93.5 (s), 83.3 (d), 52.6 (q), 52.5 (q), 38.9 (d), 23.6 (t), 22.7 (t), 12.3 (q).
MS (EI): m/z (%) = 524 (M⁺, 19), 492(100), 464(39), 432(19), 387(17), 260(23).
HRMS (EI): m/z calcd for C₂₅H₂₄N₄O₉, 524.1543; found, 524.1547.

12

CCDC 207843-207847 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/conts/retrieving.html (or from the CCDC 12 Union Road Cambridge CB2 1EZ UK; fax:[phone]; e-mail: [e-mail]).

14

2-(2-Oxo-propyl)-3,4-dihydro-2 H -azulen-1-one(5)
Yield: 28%; colorless oil.
IR(neat): 3028, 2922, 1711, 1697, 1435, 1267, 1140 cm^-1.
¹H NMR (400 MHz, CDCl₃): δ = 6.77 (d, 1 H, J = 11.1 Hz), 6.55 (dd, 1 H, J = 11.1, 5.7 Hz), 6.17 (dd, 1 H, J = 9.9, 5.7 Hz), 5.39-5.46 (m, 1 H), 3.00-3.10 (m, 2 H), 2.79-2.92 (m, 3 H), 2.52 (dd, 1 H, J = 18.0, 9.7 Hz), 2.38(d, 1 H, J = 19.6 Hz), 2.18 (s, 3 H).
¹³C NMR (100 MHz, CDCl₃): δ = 206.7 (s), 206.3 (s), 164.7 (s), 136.1 (s), 131.0 (d), 129.0 (d), 122.5 (d), 121.0 (d), 44.6 (t),43.8 (d), 37.5 (t), 31.1 (t), 29.9 (q).
MS (EI): m/z (%) = 202 (M⁺, 91), 159(100), 145(41).
HRMS (EI): m/z calcd for C₁₃H₁₄O₂, 202.0994; found, 202.0997.

15

For spectroscopic evidence of the generation of the ruthenium-carbenoid intermediate, see ref. [5j] and below:
To a solution of [Ru^II(TTP)(CO)] (50mg, 0.063mmol) in benzene (2mL) was added a solution of methyl 2-diazo-3,6-dioxoheptanoate(18.6mg, 0.094mmol) in benzene (1mL). The reaction mixture was stirred at 40 °C for 1 h, cooled to r.t. and concentrated under reduced pressure. The residue was washed with hexane and a small amount of MeOH to give the product as deep red solid (37mg, 61%) (Scheme [4] ).
¹H NMR (400MHz, CDCl₃): δ = 8.55 (s, 8 H), 7.99 (dd, 8 H, J = 10.0, 3.6 Hz), 7.49 (d, 8 H, J = 7.9 Hz), 2.67 (s, 12 H), 2.27 (s, 3 H), 1.6 (s, 3 H), 1.04 (t, 2 H, J = 6.9 Hz), -0.97 (t, 2 H, J = 6.9 Hz).
¹³C NMR (100MHz, CDCl₃): δ = 283.8 (Ru=C).
MS (FAB): m/z (%) = 940 [M + H]⁺, 770.