Gold-Catalyzed 1,4-Carbooxygenation of 3-En-1-ynamides with Allylic and Propargylic Alcohols via Non-Claisen Pathways

Article abstract of DOI:10.1002/adsc.201601092

Gold-catalyzed 1,4-carbooxygenations of 3-en-1-ynamides with allylic alcohols and propargylic alcohols yield α,β-unsaturated amides through non-Claisen pathways; the mechanisms involve ionization of the initial gold enol ethers to form C-bound gold dienolates that capture allylic or propargylic cations to yield the observed products. Our¹⁸O-labeling experiments exclude a direct gold-catalyzed allylation or propargylation on these 3-en-1-ynamides. (Figure presented.).

Full text of DOI:10.1002/adsc.201601092

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DOI: 10.1002/adsc.201601092
Gold-Catalyzed 1,4-Carbooxygenation of 3-En-1-ynamides with
Allylic and Propargylic Alcohols via Non-Claisen Pathways
Sovan Sundar Giri,a Li-Hsuan Lin,a Prakash Daulat Jadhav,a and Rai-Shung Liua,*
a
Department of Chemistry, National Tsing-Hua University, Hsinchu, Taiwan, ROC
Fax : (+886)-3-571-1082; e-mail: rsliu@mx.nthu.edu.tw
Received: October 5, 2016; Revised: November 16, 2016; Published online: && &&, 0000
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201601092.
Abstract: Gold-catalyzed 1,4-carbooxygenations of
3-en-1-ynamides with allylic alcohols and propargyl-
ic alcohols yield a,b-unsaturated amides through
non-Claisen pathways; the mechanisms involve ion-
ization of the initial gold enol ethers to form C-
bound gold dienolates that capture allylic or propar-
gylic cations to yield the observed products. Our
18O-labeling experiments exclude a direct gold-cata-
lyzed allylation or propargylation on these 3-en-1-
ynamides.
products 4 and 5 through non-Claisen pathways. Our
18O-labeling experiments exclude a direct allylation or
propargylation of 3-en-1-ynamides catalyzed by gold
complexes.[8]
Ynamides are common substrates for gold-cata-
lyzed reactions because of their high electrophilici-
ty.[9,10] Ynamides were selected as target substrates be-
cause their Lewis acid-catalyzed reactions with prop-
argylic alcohols can proceed at room temperature,[3c,d]
yielding Claisen-type products 6.[3a,b,11] We examined
the chemoselectivity of the reaction between 3-en-1-
Keywords: allylic and propargylic alcohols; 1,4-car-
booxygenation; 3-en-1-ynamides; gold catalysis;
non-Claisen pathways
The advent of gold catalysis has inspired new func-
tionalizations of alkynes with a broad range of nucle-
ophiles to afford valuable molecules.[1] Gold-catalyzed
reactions of alkynes with allylic or propargylic alco-
hols are powerful tools to access 1,5-enones I and 1,5-
allenyl ketones II,[2,3] which serve as versatile building
blocks in organic synthesis.[4,5] Such one-pot reactions
have been thoroughly examined by Aponick,[2a]
Nolan,[2b] Hsung,[2c,3a,b] and others[2,3] using gold or
acid catalysts; the mechanisms typically involve initial
hydroalkoxylations,[6] followed by Claisen rearrange-
ments[7] (Scheme 1). In the reaction mechanism, there
is no support for the participation of vinylgold ethers
A or A’ in the [3,3]-sigmatropic rearrangement before
protodeaurations, although this gold-containing rear-
rangement is calculated to possess only a small bar-
rier.[2b] Here, we report gold-catalyzed 1,4-carbooxy-
genations of 3-en-1-ynamides with allylic and propar-
gylic alcohols, yielding a,b-unsaturated amides 4 and
5 efficiently. These atypical products imply an ioniza-
tion of the initial vinylgold intermediates B and B’ to
form C-bound gold dienolates C that capture allylic
or propagylic cations to yield 1,4-carbooxygenation Scheme 1. A summary of the catalytic reactions.
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Table 1. Non-Claisen versus Claisen products.
[a]
[b]
[c]
[d]
[e]
[1a]=0.15M.
Product yields are reported after separation on a silica column.
dr>20:1 for species 6a–6c.
HNMs(n-Bu) was isolated in 61% due to a hydration of amides 1a-H or 1a-H’.
This complex is free of silver salts.
ynamides 1a with propargylic alcohols using Lewis IPrAuOTf yielded the desired 4c and hydration prod-
acid catalysts. Table 1 shows the effects of aryl sub- uct 1a-H in 26% and 62% yields, respectively
stituents of propargylic alcohol 2a–c on the chemose- (entry 5). Zn(OTf)2 gave two carbooxygenation com-
lectivitiy. Our initial tests on propargylic alcohols 2a pounds 4c and 6c, in 33% and 42% yields, respective-
and 2b (1.1 equiv.) with Ph3PAuCl/AgOTf (10 mol%) ly (entry 6) whereas highly acidic Sc(OTf)3 yielded
in dry toluene at 258C yielded 1,2-oxoallenylation compound 4c in 45% yield because of a competitive
products 6a and 6b in 77% and 40% yields, respec- hydration reaction (entry 7). Less acidic AgOTf gave
tively, corresponding to Claisen-type products (en- non-Claisen product 4c in a satisfactory yield (71%,
tries 1 and 2). Allenyl compounds 6a and 6b were entry 8). Notably, HOTf was an ineffective catalyst to
formed with high diastereoselectivity (dr>20:1); the yield 1,4-addition product 4c in 25% yield because
molecular structure of species 6a was inferred from this acid gave HNMs(n-Bu) in 61% yield (entry 9).
that of its tosylamide analogue 6a’.[12] The reactions of MeCN and DCM were also efficient solvents with
alcohols 2b with IPrAuOTf (10 mol%)[13a] afforded Ph3PAuCl/AgOTf to afford compound 4c in 77% and
additional non-Claisen compound 4b in 25% yield 76% yields respectively (entries 10 and 11). To ensure
(entry 3). With a switch to electron-rich propargylic the
catalytic
role
of
Ph3PAu+,
silver-free
alcohol 2c, Ph3PAuOTf afforded a distinct 1,4-oxopro- Ph3PAuOTf[13b] was tested in this reaction and yielded
pargylation product 4c in 91% (entry 4), whereas compound 4c in 91% (entry 12). The non-Claisen re-
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actions occur preferably with electron-rich propargyl- period (0.8 h), 3-en-1-ynamide 4d gave two isomers
ic alcohol 2c using less acidic catalysts AgOTf or with E/Z=2.7:1. These different E/Z ratios at two
LAuOTf (L=Ph3P or IPr), but AgOTf and IPrAuOTf time periods indicate that Ph3PAuOTf catalyzed the
were also troubled with hydration products 1a-H/1a- Z!E isomerization of species 4d (entries 1 and 2).
H’ (entries 5 and 8).
For propargylic alcohols 2d and 2e bearing varied al-
We assessed the scope of 1,4-oxopropargylations kynyl substituents (R6 =n-butyl and isopropyl), their
with various 3-en-1-ynamides 1 and electron-rich propargyl derivatives 4f and 4g were obtained in 58–
propargylic alcohols 2. The reactions were performed 61% yields (entries 3 and 4). 2-Thienyl-containing
with Ph3PAuCl/AgOTf in toluene; the resulting 1,4- propargylic alcohols 2f–2h (R5 =2-thienyl, R6 =Ph,
oxopropargylation products 4d–4n were present isopropyl and n-butyl) were also applicable substrates
mainly in E-configurations (E/Z> 20:1, Table 2, en- to yield propargyl species 4h–4j in moderate yields
tries 1–11). For species 1b and 1c bearing alterable (47–61%, entries 5–7). For ynamide 1d bearing
sulfonamides [NR4EWG=NTsMe, NTs(n-Bu)], their a trans-styryl group (R4 =Ph, R1 =R3 =H), the reac-
corresponding 1,4-oxopropargylation products 4d and tions with two propargylic alcohols 2c and 2f (R5 =4-
4e were produced with good yields (74–76%) and MeOC6H4 and 2-thienyl) afforded similar products 4k
high E-selectivity (E/Z>20:1) over 4 h. In a brief and 4l in satisfactory yields (65–68%), albeit in two
diastereomers (dr=4.1:1 and 2.2:1, entries 8 and 9).
For 3-en-1-ynamide 1e bearing a gem-dimethylvinyl
Table 2. Scope for Non-Claisen reactions.[a–c]
substituent (R1 =H, R4 =R3 =Me), its reactions with
two alcohol substrates 2c and 2f afforded compounds
4m and 4n in 72% and 78% yields respectively (en-
tries 10 and 11).
Our next aim was to realize novel 1,4-oxoallylations
of 3-en-1-ynamide 1a with electron-rich allylic alco-
hols 3; the results are summarized in Table 3. All re-
sulting 1,4-oxoallylation products 5 were present as E-
isomers (E/Z>20:1) except 5f with E/Z=5:1. Besides
1,4- and 1,2-oxoallylation products 5 and 7, hydration
compounds 1a-H and 1a-H’ were present but are not
reported here. Gold-catalyzed reactions of 3-en-1-yn-
AHCTUNGTREGaNNUN mide 1a with 1-phenylprop-2-en-1-ol 3a or 1,1-dime-
thylprop-2-en-1-ol 3b followed the Claisen reaction,
yielding 1,2-oxoallylation products 7a and 7b in 89%
and 63% yields, respectively (entries 1 and 2). The
use of easily ionizable 1,3-diphenylprop-2-en-1-ol 3c
enabled the desired 1,4-oxoallylation product 5c with
a yield of up to 95% (entry 3). Notably, such gold-cat-
alyzed reactions of 3-en-1-ynamide 1a with two allylic
alcohols 3d and 3e afforded the same compound 5d in
satisfactory yields (63–67%, entries 4 and 5). A 1,4-
oxoallylation of 3-en-1-ynamide 1a with tertiary allylic
alcohol 3f occurred at the less hindered allylic
carbon, yielding compound 5f in 35% yield with two
isomers (E/Z=5:1, entry 6). The reactions of this
enynACTHUNRTGNEUNGamide with 1,1-dimethyl-3-phenylpropr-2-en-1-ol
3g and 3,3-dimethyl-1-phenylpropr-2-en-1-ol 3h gave
compounds 5g and 5g’ in comparable proportions. In
the course of these reactions, Ph3PAuCl/AgOTf cata-
lyzed the isomerizations between the allylic alcohols
3g and 3h.
We also tested other 3-en-1-ynamides 1 to expand
the reaction scope; the results are summarized in
Table 4. For initial species 1b and 1c bearing alterable
sulfonamides [NR’EWG=NTsMe, NTs(n-Bu)], their
resulting 1,4-oxoallylation products 5h and 5i were
obtained with high E-selectivity (E/Z>20:1) over
a 2 h period. The reaction worked well with other 3-
[a]
[1a]=0.15M.
E/Z>20:1 for entries 2–11.
Product yields are reported after separation from a silica
column.
[b]
[c]
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Table 3. Effects of allylic alcohols on 1,2- or 1,4-addition reactions.[a–c]
[a]
[1a]=0.15M.
[b]
Product yields are reported after separation on a silica column.
E/Z>20:1 for products 5c, 5d, 5g and 5g’.
[c]
substituted 3-en-1-ynamides 1h and 1i (R1 =Ph and n- droxy oxygen of the initial allylic alcohol 3c is the
Bu, R2 =R3 =H), yielding the desired products 5j and main source of the amide oxygen of compound 18O-
5k in 70% and 92% yields, respectively; but for 4,4- 5c. Accordingly, we exclude a mechanism involving
dimethylvinyl derivative 1e, we obtained only its an initial formation of allylic cation D, followed by an
Claisen-reaction product 8c in 70% yield with dr= attack of 3-en-1-ynmide 1a because this route is ex-
10:1 (entry 5).
pected to yield 16O-5c as the major species. Similarly,
Common ynamides 1f and 1g were also applicable an SN2’ reaction between species 1a and 18O-3c is also
to these non-Claisen reactions to expand the reaction excluded. Hydration products 1a-H and 1a-H’ were
scope; we employed highly ionizable propargylic alco- inactive toward allylic alcohol 3c in the presence of
hols 2c and 2f to confirm this pathway (Scheme 2).
The reactions of these two ynamides with alcohols af-
forded 1,2-progarylation products 4o, 4p and 4q in
reasonable yields. Herein, we isolated no 1,2-
oxoallenACHTUNGTRENNUNGation product from the Claisen reactions. Un-
activated alkynes such as phenylacetylene failed to
react with propargylic alcohol under similar catalytic
conditions.
To gain mechanistic insights, we prepared 18O-con-
taining allylic alcohol 18O-3c with the content,
16O/18O=1.00:1.03. At 50% conversion in wet tolu-
ene, the resulting 1,4-oxoallylation product 18O-5c
bore the ratio 16O/18O=1.00:0.76, indicating a small
loss of 18O content (Scheme 3). At the end of reac-
tion, the 18O–H group of unreacted alcohol 18O-3c
bore the ratio, 16O/18O=1.00:0.56, due to a slow ex-
change with H2O. These results indicate that the hy- Scheme 2. The reaction with common ynamides.
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Table 4. 1,4-Oxoallylations for various 3-en-1-ynamides.[a–c]
vated ketones to enol ethers that undergo subsequent
a-alkylations with propargylic alcohols to give propy-
lation products.[14] That no reaction occurred for these
reactants is not surprising.
Scheme 4 shows a postulated mechanism to ration-
alize the 1,4-carbooxygenations of initial 3-en-1-yn-
AHCTUNGTRENNUNG
amide 1a. According to the 18O experiments, the addi-
tion of allylic alcohols and propargylic alcohols to p-
alkynes A is the initial step to yield species B or B’
respectively. With electron-rich allylic or propargylic
alcohols, species B or B’ undergoes self-ionization to
form gold enols C together with allylic or propargylic
cations. Intramolecular reactions of these pairs are ex-
pected to yield 1,4-carbooxygenation products 5c and
4c, respectively.
This model rationalizes well the side products of
some catalysts in Table 1; enolate C bearing electron-
rich IPrAu tends to undergo protonation to form hy-
dration products 1a-H or 1a-H’ (entry 5). For
Zn(OTf)2, its vinyl propargyl ether B is expected to
release HOTf to form a dual acid species D,[15b] thus
giving additional Clasien product 6c (entry 6).
[a]
[1]=0.15M.
E/Z>20:1 for entries 1–3.
Product yields are reported after separation from a silica
[b]
[c]
column.
Scheme 3. Experiments to elucidate the mechanism.
Ph3PAuCl/AgOTf under similar conditions. According
to a recent report,[14] a mixture of trimethoxymethane
and AgOTf catalyst enabled the conversion of unacti- Scheme 4. A postulated mechanism.
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To a dry toluene solution (2 mL) of Ph3PAuCl (0.023 g,
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The authors wish to thank the National Science Council,
Taiwan for supporting this work.
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COMMUNICATIONS
8 Gold-Catalyzed 1,4-Carbooxygenation of 3-En-1-ynamides
with Allylic and Propargylic Alcohols via Non-Claisen
Pathways
Adv. Synth. Catal. 2017, 359, 1 – 8
Sovan Sundar Giri, Li-Hsuan Lin, Prakash Daulat Jadhav,
Rai-Shung Liu*
Adv. Synth. Catal. 0000, 000, 0 – 0
8
ꢀ 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ÞÞ
These are not the final page numbers!