Co|d Cata|ys|s:

|ews rom t|e

|omoeneoos W|n
A. Stephen K. Hashmi, fiIiz Ata, Jan W. Bats,
M. Carmen BIanco, WoIfgang frey, MeIissa
Hamzic, Matthias RudoIph, RaIph SaIathe,
Sascha Schfer, MichaeI WIe
|nst|tot or Oran|sc|e C|em|e, On|vers|tat Stottart,
|aenwa|dr|n 55, |/0569 Stottart, Cermany
|ttp:jjwww.|as|m|.de
Abstract
PhenoI synthesis using a homogeneous goId cataIyst
serves as an exampIe of the tremendous progress
in homogeneous cataIysis by goId which has been
made in the past few years. various aspects of this
reaction, incIuding cataIyst seIectivity and activity
and the simpIe conditions used are described; and
the mechanism is discussed in this context.
S|nce t|e prev|oos CO|| 2002 conerence |n vancoover,
|nterest |n |omoeneoos cata|ys|s w|t| o|d cata|ysts |as
|ncreased s|n|cant|y. Vore t|an 50 roops are now wor||n
|n t||s e|d and t|e tota| nomber o pob||cat|ons |as |ncreased
rom |ess t|an 20 |n t|e w|o|e o 2004 to more t|an 40
dor|n t|e rst ve mont|s o 2006, w|||e 95 o t|e corrent
pob||cat|ons on o|d cata|ys|s descr|be react|ons os|n
|eteroeneoos cata|ysts. /s ar as |nnovat|on |s concerned,
t|e ap between |omoeneoos and |eteroeneoos cata|ys|s
|s becom|n sma||er (!/). |ere we sommar|se reso|ts
reported |n t|e s| posters we presented at CO|| 2006.
Background
One ocos was t|e react|on o orans w|t| term|na| a||yny|
roops |n t|e s|de c|a|n (S). 1||s was c|osen, as |t |s a beaot|o|
case stody or t|e ac||evements |n recent years.
1|e react|on was d|scovered |n 2000, and ||ore ! |nd|cates
an eamp|e o t|e ear|y reso|ts or t|e react|on o t|e most
typ|ca| test sobstrate 1 to prodoce t|e p|eno| 2.
1||s eamp|e demonstrates many o t|e eatores t|at are
typ|ca| o |omoeneoos o|dcata|ysed react|ons:
(!) W|||e |n |eteroeneoos cata|ys|s very comp|e cata|ysts
are osed |n most cases and t|e sobstrates are oten
qo|te s|mp|e sma|| mo|eco|es (e carbon mono|de),
|n |omoeneoos cata|ys|s t|e cata|yst can be re|at|ve|y
s|mp|e and t|e sobstrate tends to be comp|e.
(2) Oten severa| bonds are bro|en (oor bonds
s|own |n red |n 1) and severa| new bonds are
ormed (oor bonds s|own |n reen |n 2). 1||s d|rect
convers|on was prev|oos|y not |nown |n oran|c c|em|stry:
on|y o|d cata|ys|s a||ows t||s d|rect transormat|on
|n an ec|ent manner.
(2) 1yp|ca| cata|yst |oad|ns are somew|ere between !
and 5 mo|, w||c| corresponds to 20!00 tornovers
(tornover nomber 1O|). keact|on t|mes are oten |n t|e
rane o |oors, t|en t|e tornover reqoenc|es (1O|) are
s|n|cant|y sma||er t|an !00 |
-!
.
(4) 1|ere are nomeroos poss|b|e react|on pat|ways, bot
oten t|e c|emose|ect|v|ty |s ||| and on|y one prodoct
|s obta|ned.
(5) 1|e react|on cond|t|ons are s|mp|e and robost, and
ne|t|er abso|ote so|vents nor t|e ec|os|on o a|r |s
needed.
W|at was t|e statos o t|e /oC|
2
cata|ysed convers|on o
1 |n 2000 One coo|d sommar|ze t|e |n|t|a| eatores o t|e
o|dcata|ysed p|eno| synt|es|s as o||ows:
- ||||y se|ect|ve
- S|mp|e cond|t|ons (no abso|ote so|vents needed)
|ow cata|yst act|v|ty (1O| 4S, 1O|

!0 |
-!
)
Vec|an|sm on|nown
|onct|ona| roop to|erance ||m|ted

|ow d|d t||s |n|t|a| p|ctore c|ane over t|e |ast ew years
CoId BuIIetin 2001 40j1 31
figure 1
Co|dcata|ysed react|on o t|e test sobstrate ! to prodoce t|e p|eno| 2.
COLD 2006 PRESEN1A1ION
CoId BuIIetin 2001 40j1 32
We a|so tr|ed to ep|ore |eteroeneoos cata|ysts or t|ese
cyc|o|somer|zat|on react|ons, bot most o t|em comp|ete|y
a||ed. /mon t|e onsoccesso| cata|ysts" were /ojC, /oj
|e
2
O
2
, /ojS|O
2
, /oj1|O
2
and /onanopart|c|es. ||na||y, /ve||no
Corma prov|ded /o on nanocrysta|||ne CeO
2
. W|t| t||s
|eteroeneoos cata|yst a 1O| o 29! and a 1O| o !6 |
!
was
observed (!!).
Improving the CataIyst Activity
||rst o a|| t|e cata|yst act|v|ty orent|y needed |mprovement.
/ var|at|on o t|e meta| was not soccesso| (9): o|d cata|ysts
|ndeed are t|e best cata|ysts or t||s react|on. |nstead o
t|e s|mp|e /oC|
2
(1O| 4S, 1O|

!0) a rane o ot|er o|d

comp|ees and ot|er so|vents was eva|oated. 1||s |ed to ose
o pyr|d|netype ||ands, or eamp|e t|e an|on|c pyr|d|ne2
carboy|ato ||ands 3-6 s|own |n ||ore 2 (!0). W|t| t|ese
||ands t|e cata|yst |oad|n coo|d be redoced to as ||tt|e as
0.0/ mo|, t|e y|e|d obta|ned t|en corresponded to a 1O|
o !200.
figure 2
W|t| pyr|d|ne comp|ees 3-6 a moc| |||er cata|yst act|v|ty |s obta|ned, cata|yst 1 prov|des ev|dence or arene o|des as react|on |ntermed|ates.
figure 3
Vec|an|sm or t|e o|dcata|ysed p|eno| synt|es|s.
CoId BuIIetin 2001 40j1 33
ExpIoring the Mechanism
1|en t|e mec|an|sm |ad to be addressed. |ar|y eper|ments
|nd|cated an |ntramo|eco|ar m|rat|on o t|e oran oyen
atom, w||c| t|en becomes t|e p|eno||c oyen atom (S).
1|e brea||n o oor bonds and t|e orm|n o oor new
bonds |s c|ear|y not an e|ementary react|on w|t| on|y one
trans|t|on state. |n|t|a| eorts to detect an |ntermed|ate
os|n |ns|to noc|ear manet|c resonance tec|n|qoes at
|ow temperatore a||ed. ||t|er on|y t|e start|n mater|a|
or, at temperatores above 0C, on|y t|e na| prodoct 2
was detectab|e w|en os|n t|e /oC|
2
cata|yst. 1||s meant
t|at t|e barr|er o act|vat|on or t|e rst step |s t|e |||est
one, and once t|e mo|eco|es |ave passed t|roo| t||s,
t|ey convert to 2 |n moc| aster sobseqoent steps. 1|en
|c|avarren, w|en os|n p|at|nom cata|ysts, observed
s|deprodocts w||c| coo|d be ep|a|ned by p|at|nom
v|ny| carbeno|d |ntermed|ates ana|ooos to 10 (!2). On|y
recent|y |ave we been ab|e to ver|y t|at s|m||ar s|de
prodocts can come rom o|d cata|ysed react|ons (!2).
|rev|oos|y, w|t| t|e o|d cata|ysts, we |ad observed ot|er
s|de prodocts der|v|n rom |ater steps o t|e mec|an|sm,
and t||s on|y w|t| b|s(ory|)met|anes (!4). |n 2004 we
coo|d prove t|at arene o|des 12 are |ntermed|ates |n
t|e react|on, based a|so on ose o pyr|d|ne ||ands |n
comp|ees o type 1 rom ||ore 2 (!5). 1|os today a
re|at|ve|y deta||ed mec|an|st|c concept e|sts (||ore 2),
t|e |n|t|a| step o t|e react|on be|n s|m||ar to t|e we||
|nown enynecyc|o|somer|zat|on, w|t| t|e ort|er steps o
t|e react|on mec|an|sm ma||n t||s a prev|oos|y on|nown
mode o t|e enynecyc|o|somer|zat|on react|on - w||c|
aa|n |nd|cates t|e on|qoeness o o|d cata|ysts.
keard|n t|e oranometa|||c and oran|c |ntermed|ates
|nvo|ved, t||s |s a very |nnovat|ve type o cata|ys|s.
Expanding the functionaI Croup 1oIerance
1|e |ast po|nt to address was t|e onct|ona| roop to|erance.
|n|t|a||y sobstrates soc| as 1 |ad a tosy| protect|n roop on
n|troen, w||c| |s d|co|t to remove. |n t|e meant|me t|e
met|odo|oy |ad been app||ed to a tota| synt|es|s w||c| oses
no protect|n roop at a|| (!6,!/), and a|so carbamate protected
sobstrates |ad been osed w|t| soccess (||ore 4, 14) (!S). |ven
figure 5
Contro| o t|e c|emose|ect|v|ty by t|e c|o|ce o a so|tab|e ||and.
figure 4
||erent onct|ona| roops are to|erated.
CoId BuIIetin 2001 40j1 34
w|t| t|e s|mp|e /oC|
2
cata|yst (!S) and |n sobstrate 16 bear|n
bot| an a||yny| and an a||y| roop, t|e CC tr|p|e bond reacts
c|emose|ect|ve|y, and t|e CC doob|e bond |s not tooc|ed
onder t|e react|on cond|t|ons s|own |n ||ore 4 (!2,!9).
1|e presence o a ||and on o|d can, |owever,
somet|mes s|ow a stron |noence on t|e c|emose|ect|v|ty
o t|e process. |or eamp|e, w|t| t|e Oson|aona sa|t ,
C||/o|||
2
|
2
b|
4
(20), a m|tore o |ydroary|at|on prodoct 20
and p|eno| 19 was obta|ned rom 18 (||ore 5). Sw|tc||n
to t|e Sc|m|dbaorbay|er sa|t ,C||/o|Ves
2
|
2
b|
4
(2!) w|t| t|e
more bo||y tr|smes|ty|p|osp|ane ||and, ||| se|ect|v|ty or
t|e p|eno||c prodoct 19 was reestab||s|ed (22).
1|e react|on a|so to|erates s|n|cant ster|c ||ndrance,
an adamanty| or even a mes|ty| sobst|toent on t|e oran 22
(||ore 6, |n reen) |s to|erated w|t|oot any prob|em (22).
|ere one new CC bond (||ore 6, |n red) to t|e mes|ty|
carbon |s ormed, and t||s |s osoa||y a d|co|t tas|. /s |n
many o t|e eamp|es above, t|e stroctore o t|e prodocts
was onamb|ooos|y estab||s|ed by a s|n|e crysta| stroctore
ana|ys|s, w||c| or 21 |s s|own |n ||ore /. 1||s n|ce|y s|ows
|ow t|e two ort|o met|y| roops s||e|d t|e two carbon
atoms o t|e b|ary| |onct|on.
ConcIusions
1|e s|n|cant proress made |n |omoeneoos cata|ys|s by
o|d |n t|e past ew years |s we|| |||ostrated by t|e eamp|e
o t|e p|eno| synt|es|s descr|bed |ere: more act|ve and
more se|ect|ve cata|ysts as we|| as a ||| onct|ona| roop
to|erance |ave been ac||eved, and qo|te a ood |ns||t |nto
t|e mec|an|sm obta|ned. 1|e reso|ts a|so |||ostrate on|qoe
aspects o cata|ys|s by o|d.
AcknowIedgements
We are very rateo| to oor sponsors ||C, |onds der
C|em|sc|en |ndostr|e, and Om|core /C 8 Co |C (ormer|y
OVC, dmc
2
, |eossa).
About the Authors
A. Stephen K. Hashmi |s proessor o
oran|c c|em|stry at t|e On|vers|tat
Stottart. |e carr|ed oot ||s ||p|oma and
||| researc| w|t| |roessor C. Sze|m|es
at t|e |odw|Va|m|||ansOn|vers|tat
Vonc|en |n t|e e|d o stra|ned
oran|c compoonds soc| as a||enes,
b|cyc|obotanes and prope||anes. ||s postdoctorate researc|
w|t| |roessor b. V. 1rost at Stanord On|vers|ty, Ca||orn|a,
covered trans|t|on meta| cata|ysed react|ons |nvo|v|n
enyne metat|es|s. ||s |ab|||tat|on w|t| |ro. '. Vo|zer at
t|e |re|e On|vers|tat ber||n, t|e 'o|ann Wo|an Coet|e
On|vers|tat |ran|ort and t|e On|vers|tat W|en, /ostr|a, as
we|| as v|s|ts at t|e On|vers|ty o 1asman|a, /ostra||a, and
t|e On|vers|tat Varbor ocosed on bot| sto|c||ometr|c
oranometa|||c c|em|stry and trans|t|on meta| cata|ysed
oran|c react|ons. 1oday, |omoeneoos o|dcata|ysed
oran|c react|ons are t|e ma|or top|c |n t|e roop at
On|vers|tat Stottart.
M. C. BIanco obta|ned |er ||| |n
|orono, Spa|n, and |o|ned t|e roop or
two years as a postdoc |n t|e /Ok|C/1
k1| o t|e |oropean On|on. S|e |as now
retorned to Spa|n w|t| a 'oan de |a C|erva
e||ows||p, |n araoza s|e |s st||| wor||n
on o|d w|t| |ro. /. |aona.
figure 1
Ok1|| p|ot o t|e so||d state stroctore o 21.
figure 6
Ster|c ||ndrance does not prevent t|e o|dcata|ysed p|eno| synt|es|s.
CoId BuIIetin 2001 40j1 35
W. frey |s a spec|a||st |n `ray
crysta||orap|y at Stottart On|vers|ty.
J. W. Bats |o|ds a s|m||ar pos|t|on at
|ran|ort On|vers|ty, bot| |ave determ|ned
nomeroos stroctores or t|e roop.
f. Ata, M. Hamzic, M. RudoIph, R. SaIathe, S. Schfer
and M. WIe are ||| stodents |n t|e roop w|o a|| stod|ed
|n Stottart. S. Sc|aer |as spent s| mont|s at araoza
On|vers|ty as an |rasmos ec|ane stodent.
References
! C. |y|er, /new. C|em., 2000, 112, 440/; /new C|em. |nt. |d., 2000,
39, 422/
2 /.S.|. |as|m|, Co|d bo||., 2002, 36, 2
2 /.S.|. |as|m|, Co|d bo||., 2004, 31, 5!
4 /. /rcad| and S. || C|oseppe, Corr. Or. C|em., 2004, 8, /95
5 /. |omannkoder and |. |raose, Or. b|omo|. C|em., 2005, 3, 2S/
6 /.S.|. |as|m|, /new. C|em., 2005, 111, /!50; /new. C|em. |nt. |d.,
2005, 44, 6990
/ /.S.|. |as|m| and C.'. |otc||ns, /new. C|em., 2006, 118, S064;
/new. C|em. |nt. |d., 2006, 45, /S96
S /.S.|. |as|m|, 1. V. |rost and '. W. bats, '. /m. C|em. Soc., 2000, 122,
!!552
9 /.S.|. |as|m|, 1.V. |rost and '.W. bats, Or. |ett., 200!, 3, 2/69
!0 /.S.|. |as|m|, '.|. Weyraoc|, V. kodo|p| and |. |orpe|ov|c, /new.
C|em., 2004, 116, 6/0/; /new. C|em. |nt. |d., 2004, 43, 6545
!! S. Carrett|n, V.C. b|anco, /. Corma and /.S.|. |as|m|, /dv. Synt|. Cata|.,
2006, 348, !2S2
!2 b. Vart|nVatote, |.'. Cardenas and /.V. |c|avarren, /new. C|em.,
200!, 113, 4S90; /new. C|em. |nt. |d., 200!, 40, 4/54
!2 /.S.|. |as|m|, V. Wo|e, |. /ta, V. |amz|c, k. Sa|ate and W. |rey, /dv.
Synt|. Cata|., 2006, 348, 250!
!4 /.S.|. |as|m|, 1.V. |rost and '.W. bats, Cata|. 1oday, 2002, 12, !9
!5 /.S.|. |as|m|, V. kodo|p|, '.|. Weyraoc|, V. Wo|e, W. |rey, and
'.W. bats, /new. C|em., 2005, 111, 2S5S; /new. C|em. |nt. |d., 2005,
44, 2/9S
!6 /.S.|. |as|m|, |. ||n, |. ||sc|er, '.W. bats and W. |rey, C|em. |or. '.,
2002, 9, 4229
!/ /.S.|. |as|m| and |. Crond|, 1etra|edron, 2005, 61, 622!6226
!S /.S.|. |as|m|, |. |aoe, C. Sc|m|d, /. k|vas |ass and W. |rey, C|em. |or.
'., 2006, 12, 52/6
!9 /.S.|. |as|m|, '.|. Weyraoc|, |. |orpe|ov|c, 1.V. |rost, b. V|e|||c|, W. |rey
and '.W. bats, C|em. |or. '., 2006, 12, 5S06
20 k. Oson, /. |aona and V.v. Castr|||o, Synt|. keact. |nor. Vet.Or.
C|em., !9/9, 9, 2!/
2! /. bay|er, /. baoer and |. Sc|m|dbaor, C|em. ber.jkecoe||, !99/, 130, !!5
22 /.S.|. |as|m|, V.C. b|anco, |. |orpe|ov|c, W. |rey and '.W. bats, /dv.
Synt|. Cata|., 2006, 348, /09
22 /.S.|. |as|m|, k. Sa|at|e and W. |rey, C|em. |or. '., 2006, 12, 699!