A Recyclable Organocatalyst for Asymmetric Michael Addition

Supporting Information for:

A Recyclable Organocatalyst for Asymmetric Michael Addition

General information------1

General experimental procedure------2

Computational Details------2

NMR data and HPLC data for Michael addition products------16

NMR Spectra for new catalysts------19

HPLC spectra for Michael addition products ------22

General Methods. 1H and 13C NMR were recorded on Varian-500 instruments. Chemical shifts were reported in ppm down field from internal Me4Si.All the multiplet patterns assigned the first-order splitting patterns. Mass spectra were recorded using electrospray ionization (ESI) on LCQ Advanted MAX Mass instruments. Optical rotations were tested on a WZZ-3 polarimeter using 10mL cell with a 1 dm path length and Autopol II polarimete using 1mL cell with a 1 dm path length. HPLC analysis was measured using ChiralPak AS-H column.

Materials: Commercial reagents were used without purification except for otherwise explanation. Analytical thin layer chromatography was performed on 0.20 mm silica gel plates andsilica gel (200-300 mesh) was used for flash chromatography both purchased from Qingdao Haiyang Chem. Company, Ltd..

1.General experimental procedure for the Michael addition of cyclohexanone to nitroalkeneby chiral catalyst2 and 3.

To a solution of the amide catalyst (0.1 mmol), TFA (0.1mmol) and the nitroalkene (0.5 mmol) in Solvent (1 ml) was added cyclohexanone (5 mmol), and the solution was stirred at ambient temperature until TLC showed the nitroalkene disappeared. Ethyl acetate (10 volumes)was added and the solution was washed with water, 1N HCl, dried (Na2SO4) and concentrated to give the crude product which was purified by flash chromatography on silica gel.

Relative and absolute configurations of the products were determined by comparison with the known 1H NMR, chiral HPLC analysis, and optical rotation values.

2.General experimental procedure for the Michael addition of cyclohexanone to nitroalkene by chiral catalyst 4a and 4b.

To a solution of the catalyst (0.075mmol) in MeOH(0.5mL)was added cyclohexanone(2.5mmol) and the nitroalkene(0.5mmol), and the solution was stirred ambient temperature until TLC showed the nitroalkene disappeared. The mixture was concentrated and the residue diluted by 1mL mixture solvent (ethyl acetate-petroleum ether 1:1) to precipitate the catalyst. The catalyst was recovered by filter and washed with petroleum ether. The filtrate was concentrated to give crude product which was purified by chromatography on silica gel. Compounds 13a-i reported in Table 2 (entries 1-9) are known in literature and our spectroscopic data are in agreement with published data [1-3].

Computational Details

DFT calculations was carried out with the Gaussian 09 package[5]. The transition structure are fully optimized by B3LYP[5] method using 6-31G* basis set and have been confirmed to be a transition state geometry by the harmonic frequencies calculations at the same level of theory. The transition state was verified by the existence of imaginary frequency and the connectivity between the reactant and transition sate confirmed by intrinsic reaction coordinate (IRC)[6] calculation.

Table 1 Absolute energies (hartrees) of all computed stationary points as well as the

energies (kcal/mol) of the transition states relative to the energies of the

reactant complexes.

[a] Absolute energies in hartrees calculated at B3LYP/6-31G*+ZPVE. [b]Relative activation energies in kcal/mol

Cartesian coordinates for the transition states and reactant complexes.

Reactant Complex I

C -1.11116000 -0.74983900 -2.44627400

C -2.60095700 -0.37056800 -2.57146400

C -2.87267600 0.56216700 -1.36058500

C -0.47063300 0.51089500 -1.84702600

C -1.31152500 2.38588500 -0.46516700

C -0.10428800 3.00786100 -0.47982700

C 0.06090000 4.30546000 0.27559000

N -1.54189400 1.13146200 -1.04783400

C 2.92224400 -1.23698000 0.07759300

C 2.94294400 -2.46371700 -0.48973900

N 1.80441100 -3.32879200 -0.46383900

O 0.68822700 -2.93955100 0.04168600

O 1.94836200 -4.48191800 -0.96020900

C -3.57013600 -0.14051100 -0.16673700

H -0.66690400 -1.01775800 -3.41003000

H -0.98662800 -1.60687000 -1.77664200

H -2.76425400 0.19104100 -3.49960800

H -3.25617000 -1.24364600 -2.57041400

H -3.56820300 1.35784400 -1.66740400

H -0.13326000 1.20682400 -2.63445000

H 0.39675000 0.29101600 -1.21403100

C -2.43185700 3.09570500 0.27633100

H 0.76235100 2.57629600 -0.96678800

H 2.01246400 -0.91024000 0.57280200

H 3.77393700 -2.92489100 -1.00110500

C -2.48064400 4.60428400 -0.08466000

H -2.26401200 2.97748100 1.35671100

H -3.41105700 2.65809600 0.06331300

C 4.01205900 -0.27417100 0.10200900

C 5.30136200 -0.53544900 -0.41650300

C 3.74927000 0.99202600 0.67477700

C 6.29216400 0.44168500 -0.36325000

H 5.52777900 -1.50194400 -0.85437200

C 4.74505300 1.96862400 0.72247700

H 2.75819500 1.19877600 1.06816300

C 6.01704000 1.69579500 0.20519600

H 7.27930200 0.23216000 -0.76133200

H 4.53013800 2.93711400 1.16055200

H 6.79280100 2.45354900 0.24331500

C -1.09119300 5.30314800 -0.02146200

H -2.88975000 4.69762800 -1.09849800

H -3.19232300 5.10326500 0.58517800

H 1.02246000 4.77375500 0.03196500

H 0.08209800 4.11122200 1.36199300

H -1.09402900 6.09339900 0.74047600

H -0.89081300 5.79274700 -0.98232200

H -3.80913100 0.60316900 0.59992500

H -4.51150500 -0.56349000 -0.53999800

C -2.00270700 -2.51561900 2.35785800

C -2.37936000 -3.44772800 1.18409400

H -0.95540500 -2.63213500 2.64768400

H -2.60872700 -2.72104400 3.24381800

H -1.50256500 -3.92904200 0.73819300

H -3.08175800 -4.23655600 1.46638500

C -3.02735500 -2.55109200 0.14236400

O -3.63683800 -2.92178800 -0.87933600

N -2.84122800 -1.22789600 0.50578200

C -2.29151400 -1.05309900 1.86171000

C -1.05745800 -0.14872300 1.91947800

O -1.03403500 0.90294200 2.55627500

O 0.07146300 -0.59841000 1.28473600

H -0.00335600 -1.44172900 0.77396900

H -3.03229900 -0.55590600 2.49787100

TSA

C 0.33471500 -0.90293700 3.74099300

C 1.76150800 -0.42917400 3.40990100

C 1.60425800 0.55145100 2.21552700

C -0.37790100 -0.88354500 2.38207200

C -0.51416900 1.22779600 1.00350200

C -1.90560100 1.05682000 0.75165400

C -2.79340800 2.27809300 0.48132900

N 0.21021500 0.30854800 1.69129400

C -2.18254600 -0.14656600 -1.00687800

C -1.20287400 -1.14506500 -1.17502100

N 0.03674700 -0.83029100 -1.63586900

O 0.35294700 0.45019700 -1.76425300

O 0.88421100 -1.75183100 -1.94345000

C 2.80166900 0.55712800 1.23094700

H -0.15971000 -0.21235600 4.43597400

H 0.32412800 -1.90055100 4.18811300

H 2.24338300 0.07415300 4.25432700

H 2.36714100 -1.28321800 3.11067300

H 1.60562300 1.57477300 2.61604500

H -1.45675200 -0.77388900 2.48219800

H -0.14031200 -1.77537500 1.80284000

C 0.20166800 2.49046000 0.55067300

H -2.39871800 0.29571500 1.34253600

H -2.04061300 0.74231300 -1.61391300

H -1.36704800 -2.19882900 -1.01460200

C -0.70265100 3.48015200 -0.19942200

H 1.04523000 2.22916900 -0.09009500

H 0.61055500 2.99198900 1.44250600

C -3.58977700 -0.58183500 -0.81302500

C -3.92122700 -1.65213200 0.04379200

C -4.62900700 0.06263100 -1.51194900

C -5.24695300 -2.06247600 0.19461600

H -3.13589000 -2.16055000 0.59539200

C -5.95708500 -0.35009700 -1.36209600

H -4.39050300 0.87377500 -2.19285300

C -6.27095400 -1.41201100 -0.50754600

H -5.48322700 -2.88830600 0.85810200

H -6.74271000 0.15416700 -1.91549400

H -7.30099600 -1.73242700 -0.39003500

C -2.04470700 3.62254600 0.52660900

H -0.18520800 4.44287200 -0.27803700

H -0.86390500 3.12117300 -1.22368800

H -3.61529800 2.28042900 1.20876000

H -3.27565700 2.18846700 -0.50191900

H -2.66107400 4.40585500 0.06966200

H -1.86622100 3.92543600 1.56901100

H 2.78453700 1.49405000 0.67097800

H 3.69229100 0.60873400 1.88104800

C 3.99687000 -1.51853900 -1.68416300

C 3.43611600 -2.60594000 -0.75270700

H 3.29141200 -1.34342000 -2.49917100

H 4.97700000 -1.75414400 -2.10355800

H 2.75898600 -3.29891600 -1.25205100

H 4.23008500 -3.18855900 -0.26539500

C 2.68451500 -1.84480800 0.32774500

O 1.94705800 -2.36053200 1.19586900

N 3.00650700 -0.50432500 0.23271400

C 4.06829500 -0.25841200 -0.77658800

C 3.92752300 1.05692800 -1.54810900

O 4.92943300 1.74788500 -1.76705700

O 2.70827000 1.42826500 -1.99221300

H 1.88984400 0.82679200 -1.88996000

H 5.04433700 -0.19152800 -0.27668100

Reactant complex II

C -1.01992100 -0.61845000 3.36329300

C -0.23849600 -0.61797500 2.03247800

C -1.33275800 -0.80522800 0.95022000

C -2.31809100 0.11852100 3.00314000

C -3.58272300 0.41435400 0.88879100

C -4.48813900 1.23867100 1.47753600

C -5.60218600 1.81164600 0.63293200

N -2.52673500 -0.19353100 1.58039800

C 3.26184500 1.43930700 -0.26359800

C 4.36763400 1.56186400 0.50327900

N 5.12302500 0.41338100 0.89716800

O 4.77379900 -0.75943300 0.51014600

O 6.14194800 0.61176600 1.61866700

C -1.59712400 -2.29589600 0.59362400

H -0.47242100 -0.13021600 4.17491600

H -1.23791700 -1.64529600 3.68187500

H 0.26085900 0.34719900 1.88650800

H 0.53083600 -1.39482200 2.00392700

H -1.05908900 -0.27962800 0.02898700

H -2.21480300 1.20766400 3.14909400

H -3.17655800 -0.20822800 3.60335400

C -3.78337600 0.14001300 -0.59207200

H -4.44834500 1.49102200 2.53093700

H 2.96067400 0.43818400 -0.56584600

H 4.79137800 2.47148900 0.90026200

C -4.01213300 1.46142400 -1.37376300

H -4.67320100 -0.49674900 -0.71388700

H -2.96367700 -0.41757800 -1.04809600

C 2.39582300 2.51726500 -0.71561200

C 2.66330500 3.88594200 -0.48017300

C 1.22318000 2.16223300 -1.42292700

C 1.78303800 4.86398600 -0.93619700

H 3.56098800 4.18228100 0.05238400

C 0.34280300 3.14700500 -1.87459900

H 1.01515600 1.11175500 -1.60035600

C 0.62004700 4.49775300 -1.63263400

H 1.99748700 5.91157900 -0.75314500

H -0.55577500 2.86258300 -2.41162000

H -0.06344900 5.26383400 -1.98392700

C -5.06070700 2.39707100 -0.70078200

H -3.04973500 1.98464800 -1.45138200

H -4.31584400 1.21308200 -2.39805200

H -6.14324200 2.58979700 1.18434200

H -6.35066400 1.03580700 0.39240300

H -5.89828600 2.58884100 -1.38420200

H -4.59836600 3.36875800 -0.48747900

H -2.60737000 -2.38404900 0.18788700

H -1.54049600 -2.91104200 1.50110300

C 0.64714300 -3.36547200 -0.16001300

C 0.90950400 -4.30195400 -1.38736200

H 0.70187200 -3.90452800 0.78888200

C 0.04811200 -3.67506200 -2.50144200

H 1.97178200 -4.37055900 -1.63315400

H 0.55292500 -5.30689700 -1.13996500

H 0.60878800 -2.93883100 -3.08917600

H -0.37506400 -4.40458000 -3.19560200

N -0.70160800 -2.86462400 -0.41899500

C -1.06767200 -2.95656900 -1.74874700

O -2.13274000 -2.52204200 -2.22773900

C 1.68620500 -2.25131300 -0.15010300

O 1.60078300 -1.21189900 -0.82610600

O 2.73923600 -2.55582000 0.64141100

H 3.47270300 -1.87750300 0.61639100

TSB

C -1.20248900 -2.55787500 1.82257400

C 0.18843900 -2.67898900 2.34547800

C 0.67401500 -1.21931000 2.39394700

C -1.42909500 -1.26489100 1.09275700

C 0.29189000 0.58222800 0.70327000

C 1.64329500 1.01390500 0.74004900

C 1.90341600 2.43639300 0.26387200

H -1.88805400 -3.38902800 1.71552200

H 0.80839100 -3.27005600 1.65114800

H 0.24642700 -3.16440800 3.32734500

H 1.73373900 -1.13119500 2.16729000

H -1.46654700 -1.44627600 0.01453600

C -0.60876300 1.41885300 -0.16660700

H 2.28489800 0.67007700 1.54251300

N -0.14819700 -0.50854700 1.36520800

C 2.52898500 -0.25816700 -0.78367300

C 2.08799500 -1.59134700 -0.67927600

H 2.64742000 -2.37847200 -0.19796300

H 2.04617000 0.32583400 -1.56172000

N 0.89461500 -2.00615100 -1.20137300

O 0.13831200 -1.13228300 -1.85639100

O 0.50382600 -3.22693100 -1.05506500

H 0.48669600 -0.76197500 3.37450700

C -2.78167600 -0.61895300 1.54679800

H -1.62469800 1.04185900 -0.19732100

H -0.22908800 1.36612400 -1.19285100

C -0.60996100 2.90807200 0.30946800

C 3.96185700 0.05510500 -0.54681900

C 4.60697400 1.00700100 -1.36050200

C 4.71455000 -0.58421200 0.45949100

C 5.96124700 1.30497800 -1.18029700

H 4.04578000 1.50141700 -2.14726600

C 6.06636100 -0.28588600 0.64027100

H 4.23906300 -1.31437300 1.10778200

C 6.69613100 0.66024700 -0.17952000

H 6.44101700 2.03616300 -1.82292900

H 6.62929000 -0.78897400 1.42010200

H 7.74693100 0.89102100 -0.03821700

C 0.79018600 3.38306500 0.77917900

H 1.92153400 2.48780400 -0.83578700

H 2.88772400 2.77072100 0.60468700

H 0.98228600 4.40762600 0.43847000

H 0.83242400 3.40295900 1.87591500

H -0.95715100 3.51702900 -0.53351000

H -1.34704000 3.02627700 1.10933200

H -3.38963600 -1.43010800 1.96943800

H -2.60961100 0.11741700 2.33727600

C -4.16668100 -0.58399900 -0.68220200

C -5.38416500 0.31946900 -1.00839800

C -5.02389800 1.68938100 -0.39666200

H -5.56288700 0.37162500 -2.08345600

H -6.27728600 -0.09251100 -0.52678100

H -4.51866900 2.33096600 -1.12706700

H -5.87938300 2.23829800 0.00351200

C -4.04999200 1.35466200 0.72264800

O -3.69842400 2.09332300 1.66488500

N -3.58560200 0.06331800 0.52704300

H -4.43962300 -1.61923300 -0.46074600

C -3.11609800 -0.56684000 -1.80153100

O -2.90665600 0.42456400 -2.51350100

O -2.40390000 -1.71815600 -1.84313900

H -1.43622700 -1.61842000 -2.15011700

TSC

C -2.25432400 -1.57654200 1.86183900

C -1.46505000 -2.33974100 0.77750200

C -0.84883200 -1.23674200 -0.10965200

C -1.42499800 -0.31017200 2.11811600

C 0.25964000 0.88934000 0.71407400

C 1.30235200 0.82396400 -0.27165400

C 1.94908100 2.13733700 -0.72033100

N -0.63878300 -0.10053100 0.85653200

C 2.72883500 -0.27885500 0.56616300

C 2.22749800 -1.48367000 1.13913800

N 1.63703600 -1.49428900 2.37088400

O 1.53493200 -0.37216400 3.04692200

O 1.15711000 -2.60300400 2.84787900

C -1.66642100 -0.83573500 -1.36473300

H -2.35712800 -2.16808400 2.77493900

H -3.25675400 -1.31500600 1.50907700

H -0.65413400 -2.89784500 1.25673900

H -2.08897600 -3.02113700 0.19716200

H 0.12156100 -1.56390100 -0.48542900

H -0.69017500 -0.44534400 2.92357100

H -2.04987900 0.56010200 2.32700200

C 0.23033400 2.03704700 1.71285800

H 1.11026600 0.16104600 -1.11145900

H 3.02262900 0.46100200 1.30843200

H 2.28223100 -2.44760900 0.65744100

C 0.79445700 3.35941700 1.15541900

H 0.82099500 1.72293200 2.58121300

H -0.79346900 2.19454400 2.06368900

C 3.71534600 -0.44445700 -0.54987300

C 4.93000100 0.26637300 -0.52281100

C 3.47720300 -1.31747400 -1.62919400

C 5.88120300 0.10374200 -1.53589400

H 5.13447300 0.93654600 0.30700800

C 4.42536700 -1.47980100 -2.64262600

H 2.54705400 -1.87681700 -1.67431000

C 5.63202600 -0.76952200 -2.60007900

H 6.81477400 0.65569200 -1.49117600

H 4.22447500 -2.16022200 -3.46426300

H 6.36814200 -0.89652400 -3.38726400

C 2.12703200 3.14713200 0.42516200

H 1.32031400 2.59252600 -1.50281600

H 2.91255100 1.92416400 -1.19396300

H 2.50579400 4.09752500 0.02938500

H 2.87651100 2.78169000 1.14031800

H 0.07671600 3.82017000 0.45475200

H 0.90567200 4.07205600 1.98095000

H -1.17971500 0.00932700 -1.86344600

H -1.63290200 -1.70016400 -2.03993600

C -3.61135300 0.88093800 -1.38540800

C -5.12300400 0.72458800 -1.07009900

H -3.43683300 1.19864900 -2.42156900

C -5.42660900 -0.75100300 -1.38554500

H -5.27756800 0.93474500 -0.00786300

H -5.72507700 1.42712300 -1.65082600

H -6.14143200 -1.20852000 -0.69733600

H -5.81810800 -0.89134500 -2.40087300

N -3.08359300 -0.48814700 -1.18193600

C -4.07794800 -1.45046100 -1.29329700

O -3.86797400 -2.67523500 -1.35991100

C -2.94082300 1.89583500 -0.47835500

O -3.18541500 2.08166700 0.71585500

O -1.99444200 2.61948400 -1.16595300

H -1.54439700 3.26825100 -0.58015200

TSD

C -2.08289500 2.15037400 -1.85465100

C -2.31710200 3.44365300 -1.06075400

C -1.36431600 3.32702200 0.14291000

C -1.82688300 1.09837700 -0.75624700

C -0.00607400 1.48076000 1.08331400

C 0.77382200 0.28524200 0.98317000

C 1.40923600 -0.17837500 2.29862200

H -1.18816600 2.25250400 -2.48021600

H -2.93430400 1.86904700 -2.48078100

H -3.36143300 3.50811200 -0.73151200

H -2.09110500 4.33428400 -1.65122400

H -1.83946300 3.65183300 1.07381600

H -2.78022900 0.92359200 -0.23324700

C 0.36037200 2.35085900 2.26931400

H 0.37852900 -0.51936100 0.37732300

N -0.97090100 1.87401900 0.22401400

C 2.31349000 0.76870300 -0.21058400

C 1.85678900 1.37685900 -1.40910100

H 1.78336600 0.87928800 -2.36360600

H 2.73680600 1.47982700 0.49700400

N 1.47784100 2.69244500 -1.40623800

O 1.59727000 3.38675900 -0.29458400

O 0.99246700 3.23507900 -2.48171700

H -0.43205400 3.88355000 -0.01253300

C -1.35656600 -0.21833300 -1.37304700

C 0.11149000 1.58307800 3.60634800

C 0.45815900 0.07597600 3.49013300

H 1.42427000 2.59701400 2.18233300

H -0.16848000 3.30185100 2.28099900

H -0.93358300 1.70760300 3.91498100

H 0.72570300 2.05653700 4.38193800

H 0.90928800 -0.28563300 4.42216500

H -0.45935600 -0.51043900 3.33944000

H 1.67007300 -1.23849600 2.22763500

H 2.35322700 0.35423700 2.48606700

C 3.08252800 -0.50948400 -0.31078600

C 4.27186400 -0.65607800 0.42979600

C 2.67161700 -1.57263900 -1.13758100

C 5.03282500 -1.82608100 0.34282400

H 4.60881300 0.15995200 1.06258100

C 3.42874700 -2.74495100 -1.21800300

H 1.75320400 -1.50801100 -1.71011600

C 4.61245000 -2.87658100 -0.48098200

H 5.95162100 -1.91471800 0.91432700

H 3.08566700 -3.55326300 -1.85556500

H 5.20010800 -3.78680500 -0.54825900

H -1.94635500 -0.35384000 -2.28783100

H -0.31069400 -0.14997400 -1.67678700

C -2.47815600 -1.58170000 0.55389600

C -2.12040400 -2.99012400 1.13416900

C -1.50281200 -3.73935800 -0.06189400

H -1.38082100 -2.85969500 1.93015000

H -2.99519600 -3.48068100 1.56410600

H -0.68274000 -4.40658500 0.21317900

H -2.24347300 -4.33746400 -0.60746100

H -2.34483300 -0.80784300 1.31675100

C -3.92086900 -1.51839800 0.07316800

O -4.30128900 -1.44164200 -1.09593100

O -4.78909700 -1.55647300 1.14164800

H -5.72214300 -1.52606300 0.83649700

N -1.52930900 -1.42903000 -0.54701700

C -1.00168400 -2.63230200 -0.98031900

O -0.25478200 -2.75639700 -1.96938600

Reference:

1. Vanderesse R, Grand V, Limal D, Vicherat A, Marraud M (1998)JAmChemSoc 120: 9444

2. (a)S Luo, X Mi, L Zhang, S Liu, H Xu, J-P Cheng, (2006)Angew Chem Int Ed 45:3093(b)Y JCao, H H Lu, Y Y Lai, L Q Lu, W J Xiao (2006) Synthesis 22:3795

3. (a)T Ishii, S Fujioka, Y Sekiguchi, H Kotsuki, (2004) J Am Chem Soc126:9558-9559 (b)J M Betancort,K Sakthivel, R Thayumanavan, F Tanaka, C F Barbas III(2004)Synthesis 9:1509 (c) B List, P Pojarliev, H J Martin (2001) Org Lett3:2423

4. (a) A J A Cobb, D A Longbottom, D M Shaw, S V Ley (2004) Chem Commun16:1808 (b) A J A Cobb, D M Shaw, D A Longbottom, J B Gold, S V Ley (2005)Org BiomolChem3:84 (c) C E T Mitchell, A J A Cobb, S V Ley(2005)Synlett1:611

5. Gaussian 09, Revision D.01, M J Frisch, G W Trucks, H B Schlegel, G EScuseria, M A Robb, J R Cheeseman, G Scalmani, V Barone, B Mennucci,G A Petersson, H Nakatsuji, M Caricato, X Li, H P Hratchian, A F Izmaylov, J Bloino, G Zheng, J L Sonnenberg, M Hada, M Ehara, K Toyota, R Fukuda, J Hasegawa, M Ishida, T Nakajima, Y Honda, O Kitao, H Nakai, T Vreven, J A Montgomery, Jr, J E Peralta, F Ogliaro, M Bearpark, J J Heyd, E Brothers,K N Kudin, V N Staroverov, T Keith, R Kobayashi, J Normand, K Raghavachari, A Rendell, J C Burant, S S Iyengar, J Tomasi, M Cossi, N Rega, J M Millam, M Klene, J E Knox, J B Cross, V Bakken, C Adamo, J Jaramillo, R Gomperts, R E Stratmann, O Yazyev, A J Austin, R Cammi, C Pomelli, J W Ochterski, R L Martin, K Morokuma, V G Zakrzewski, G A Voth,P Salvador, J J Dannenberg, S Dapprich, A D Daniels, O Farkas, J B Foresman, J V Ortiz, J Cioslowski,D J Fox (2013) Gaussian, Inc, Wallingford CT

6. C Gonzalez, H B Schlegel (1990)J Phys Chem94:5523

NMR data and HPLC data for Michael addition products

13a

1H NMR (500 MHz, CDCl3) δ= 1.10-1.23 (1H, m), 1.43-1.73 (4H, m), 1.97-2.05 (1H, m), 2.26-2.45 (2H, m), 2.57-2.66 (1H, m), 3.65-3.73 (1H, m), 4.56 (1H, dd, J 12.5, 9.9 Hz), 4.87 (1H, dd, J 12.5, 4.5 Hz), 7.07-7.28 (5H, m);

The enantiomeric excess was determined by chiral HPLC with a Chiralpack AS-H column at 238nm (hexane:2-propanol 90:10), 0.7 ml/min; tr= 24.1min (minor), 34.5 min (major).

13b

1H NMR (500 MHz, CDCl3) δ : 1.20~1.28 (1H, m), 1.57~1.81 (4H, m), 2.03~2.11 (1H, m), 2.32 (3H, s), 2.36~2.42 (1H, m), 2.46~2.50 (1H, m), 2.64~2.70 (1H, m), 3.70~3.75 (1H, m), 4.59~4.63 (1H, m), 4.90~4.94 (1H, m) , 7.04 (2H, d, J=8.0 Hz) , 7.12 (2H, d, J=8.0 Hz).

The enantiomeric excess was determined by chiral HPLC with a Chiralpack AS-H column at 238nm (hexane:2-propanol 90:10), 0.7 ml/min; tr= 16.9min (minor), 31.2 min (major).

13c

1H NMR (500 MHz, CDCl3) δ : 1.19~1.28 (1H, m), 1.57~1.82 (4H, m), 2.05~2.11 (1H, m), 2.36~2.42 (1H, m), 2.46~2.50 (1H, m), 2.62~2.68 (1H, m), 3.69~3.74 (1H, m), 3.79 (3H, s), 4.57~4.61 (1H, m), 4.90~4.93 (1H, m) , 6.84 (2H, d, J=8.5 Hz) , 7.06 (2H, d, J=8.5 Hz).

The enantiomeric excess was determined by chiral HPLC with a Chiralpack AS-H column at 238nm (hexane:2-propanol 90:10), 0.7 ml/min; tr= 16.9min (minor), 31.2 min (major).

13d

1H NMR (500 MHz, CDCl3) δ : 1.30~1.38 (1H, m), 1.59~1.85 (4H, m), 2.09~2.14 (1H, m), 2.37~2.43 (1H, m), 2.47~2.51 (1H, m), 2.90~2.97 (1H, m), 4.27~4.31 (1H, m), 4.87~4.94 (2H, m), 7.20~7.25 (3H, m) , 7.38~7.39 (1H, m).

The enantiomeric excess was determined by chiral HPLC with a Chiralpack AS-H column at 238nm (hexane:2-propanol 90:10), 0.7 ml/min; tr= 20.6min (minor), 28.6 min (major).

13e

1H NMR (500 MHz, CDCl3) δ : 1.19~1.28 (1H, m), 1.57~1.83 (4H, m), 2.08~2.13 (1H, m), 2.35~2.42 (1H, m), 2.46~2.51 (1H, m), 2.63~2.68 (1H, m), 3.74~3.79 (1H, m), 4.59~4.63 (1H, m), 4.92~4.96 (1H, m) , 7.11~7.14 (2H, m) , 7.29~7.32 (2H, m).

The enantiomeric excess was determined by chiral HPLC with a Chiralpack AS-H column at 238nm (hexane:2-propanol 90:10), 0.7 ml/min; tr=22.7min (minor), 37.9 min (major).

13f

1H NMR (500 MHz, CDCl3) δ : 1.30~1.38 (1H, m), 1.60~1.86 (4H, m), 2.10~2.15 (1H, m), 2.35~2.42 (1H, m), 2.46~2.51 (1H, m), 2.84~2.92 (1H, m), 4.11~4.24 (1H, m), 4.86~4.92 (2H, m) , 7.17 (1H, d, J=8.0 Hz) , 7.23 (1H, dd, J1=8.0 Hz, J2=2.0 Hz), 7.41 (1H, d, J=2.0 Hz).

The enantiomeric excess was determined by chiral HPLC with a Chiralpack AS-H column at 238nm (hexane:2-propanol 90:10), 0.7 ml/min; tr=16.5min (minor), 25.9 min (major).

13g

1H NMR (500 MHz, CDCl3) δ : 1.19~1.28 (1H, m), 1.57~1.82 (4H, m), 2.05~2.11 (1H, m), 2.36~2.42 (1H, m), 2.46~2.50 (1H, m), 2.62~2.68 (1H, m), 3.69~3.74 (1H, m), 3.79 (3H, s), 4.57~4.61 (1H, m), 4.90~4.93 (1H, m) , 6.84 (2H, d, J=8.5 Hz) , 7.06 (2H, d, J=8.5 Hz).

The enantiomeric excess was determined by chiral HPLC with a Chiralpack AS-H column at 238nm (hexane:2-propanol 93:7), 0.7 ml/min; tr=37.4min (minor), 78.6 min (major).

13h

1H NMR (500MHz, CDCl3) δ 7.33−7.25 (m, 3H), 7.15−7.14 (m, 2H), 4.65 (1H, dd, J1=12.4Hz, J2=9.1Hz), 4.58 (1H, dd, J1=12.4Hz, J2= 4.8Hz), 3.73−3.68 (m, 1H), 3.01−2.94 (m, 1H), 2.63–2.54 (m, 1H), 2.43−2.35 (m, 1H), 1.05 (3H, t, J=7.3Hz), 0.95 (3H,d, J=7.1Hz,).

The enantiomeric excess was determined by chiral HPLC with a Chiralpack AS-H column at 238nm (hexane:2-propanol 90:10), 0.7 ml/min; tr=14.1min (minor), 18.6 min (major).

13i

1H NMR (500 MHz, CDCl3) δ : 0.82~0.91 (3H, m), 1.48~1.55 (2H, m), 2.66~2.72 (1H, m),3.77~3.82 (1H, m), 4.61~4.75 (2H, m), 7.18~7.22 (2H, m), 7.29~7.37 (2H, m), 9.73 (1H, d, J=2.5 Hz).

The enantiomeric excess was determined by chiral HPLC with a Chiralpack AS-H column at 238nm (hexane:2-propanol 99:1), 2.0 ml/min; tr=28.6min (minor), 30.8 min (major).

NMR Spectra for New Catalysts

1HNMR of 3

13CNMR of 3

1HNMR of 4a

13CNMR of 4a

1HNMR of 4b

13CNMR of 4b

HPLC Spectra for Michael products

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