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doc1

Ynamines in Synthesis

IBS Baran Seminar January 23, 2008

I.B. Seiple

Baran Group Meeting 1/23/2008

General Outline

I II III IV V
- Ynamines - A Brief History - General Reactivity - Preparation of Ynamines - Ynamine Methodologies - Ynamines in Total Synthesis
- More reactive than their counterparts the ynol ethers due to lack of electronegative O atom - Usually colorless liquids (sometime solids) that are usually moisture sensitive - Very reactive species in general, but usually thermally stable - Ynamides retain stability but reactivity is attenuated - Reactivity as a function of N substitution: alkyl > morpholino > aryl/alkyl > bisaryl > (CF3)2 - Reactivity as a function of C substitution: H > alkyl > aryl > Si > COOR
III - Preparation of Ynamines I - Ynamines - A Brief History
-First report of an Ynamine in 1892 by J. Bode (Liebigs Ann. Chem. 267, 268) -Other reports in 1943 and 1951 -In 1958, all previous reports had been proven false, and Zaugg et. al reported an accidental synthesis of an ynamine (JOC 23 1389): Three methods to prepare ynamines: A) Elimination B) Substitution C) Isomerization Also, ynamides are sometimes more easily prepared (D)
A - Ynamines by Elimination
- From chloroenamines (Neuenschwander, Helv. Chim Acta 82, 326):

Cl Ph Cl Cl Cl Cl NMe2

2eq BuLi Bu3SnCl

n-BuLi

Ph Cl N N Cl N X Cl

NaH, HCONMe2

-In 1960, Wolf and Kowtz cast doubt on Zaugg's report, and claimed the first ynamine for themselves (Liebigs Ann. Chem. 638 33): 1.7% -However, in 1965 Dumont reproduced Zaugg's work and proved the 1958 ynamine -First general method of synthesis by Viehe in 1963 (ACIE 2, 477) -Since this date, ynamines have been extensively studied and reviewed: - Viehe - ACIEE 6, 767 - Viehe - Chemistry of Acetylenes, Marcel Dekker: NY, 1969; Ch. 12, pp 861-912 - Ficini - T 32, 448 - Pitacco - The Chemistry of Funcitonal Groups John Wiley & Sons: NY, Ch 15, pp 623-713 - Collard-Motte - Top. Curr. Chem. 130, p 89 - Himbert - Methoden Der Organischen Chemie (Houben-Weyl)Georg Thieme: Stuttgart, pp. 3267 - Hsung - T 57, 7575

NEt2 R Cl NR12

LiNR22 + COCl2
- From amide chlorides (Viehe, ACIE 5, 584):

O R NR12

NR*2 NR*2 NR*2 X
- From carbazoles and trichloroethylenes (Chrzaszcz, B.S.C. Belg. 104, 117):

TEBACl, NaOH

Mg, THF

Cl Cl Cl

55 - 87%

II - General Reactivity

R2N R1 R2N B A

R1 R2N

Nu: E+ B-

If R = H

R1 N R1
(same method also works to make N-ethynylpyrrole)
- "push-pull" enamines from vinyligous amides (Dell, J.C.S. Perkin Trans. 1, 3055) A+

R2N R1

Br2, Et3N DCM

Br R2N R1 O

t-BuOK, THF

15 - 69%

O R2N R1

BuLi, Et2O; R1(O)Cl

- "push-pull" ynamines from trichloroenamines and acid chlorides (pp. 1 Neueschwander ref.):

Cl Cl Cl NR2

O NR2 R1
From tertiary amines and haloalkynes (Viehe, ACIEE 3, 582) NR3

X = Cl or Br Principle:

40h, 55 C
C - Ynamines by Isomerization
- From esters and lithioaminals (Katritzky, JOC 62, 4142):

NR2 R1

N Li N O R OMe N N
When R = aryl, this can be done with KOH in DMSO For R = alkyl:

R1 NR2

NR2 N N N N NNHTs

6 eq. BuLi

Al2O3, KNH2, 50 - 80 C 60 - 90%
D - Special Syntheses of Ynamides
From chiral enamides (Hsung OL 1, 1237)

TsNHNH2, TsOH, PhH

-78 to rt 42%

O N R R1

NBS or Br2, heat X 67 - 85%

40 - 88%

- From benzotriazoloketones (Katritzky, OL 2, 3789): a) Tf2O, 2,6-Lut R > 88% R

N R R1 Br

~ 8:1 E/Z
NaOMe, MeCN or NaOH/THF > 90%
X = O, NMe, CH2 R = Ph or pentyl R1= iPr or Ph
B - Ynamines by Substitution
Nucleophilic substitution on haloalkynes by metal amides -More facile on fluoroalkynes than chloroalkynes (different mechanisms) LiNR2 LiNR2 usually > 60%
Tosylynamides from 2 tosylamines (Brckner, Synlett 2000, 1402)

formylation 85 - 99%

PPh3, CCl4, THF

R Cl Cl

NR2 NR2
A = vinyl, phenyl, EWG; X = Cl, sometimes even OMe - A can be alkyl (even tBu), but heat and very polar solvents required Most recently, X can be (IPh)+ OTf, Prepared from stannyl alkynes and Stang's reagent, >15 examples (Stang, JACS 115, 2590) -these alkynes are so reactive that often a lithium amide is not necessary, just base. Chiral TMS ynamines from dichloroacetylene (Pericas, JOC 65, 7291)

Alkynyl isocyanates from alkynylacids 1) (COCl)2
2) NaN3, heat Acetyl bromides and amides (Hsung, JOC 71, 4170; Danheiser OL 5, 4011) R CuX, base H
1) R2NH, Et2O, -70 to reflux 2) 2 eq BuLi, -70 to -10 C 3) TMSCl, -10 to rt

HNR2 =

X NH X

X = OR, H

OMe NH

Ph NH Ph

rt to 75 C Finally, from terminal alkynes and "amides" (Stahl, JACS 130, 833)

N EWG R2

70 - 96%

20% CuCl2, 2eq py.

2eq Na2CO3, 1atm O2 toluene, 70 C
- Ynamines react with acidic CH's (see Ficini Review):
IV - Ynamine Methodologies
A - Addition Reactions B - "Cycloadditions" 1. - [2 + 1] 2. - [2 + 2] 3. - [4 + 2] 4. - [3 + n] C - Functioalizations
Et2N Et2N O R O R O Me Me O

H3O+, heat

O R O Et

A - Addition Reactions

-Electron-rich ynamines react readily with water:
O R2N R1 O R O O R R2 O O H N R1 O R

CO2Me Et NEt2

-This has been taken advantage of in anhydride synthesis and peptide coupling:

O R O NH2 R1 OH

Me O Et2N

R = alk or Ar

O O Me

R2N OH

Very careful reagent control needed to achieve high yields. See reviews for details.
-Ynamines react with allylic and propargylic alcohols to give 4-alkenyl amides:
- Reaction with anhydrides: TFAA

R1 R2N O

Et2N O
- Hsung applied this stereoselectively with ynamides (OL 4, 1383):
O X N Ph O X N Ph Alk Alk
PNBSA (0.2 eq) 70-80 C >80% de

O X O N Ph Alk R1

- Reginato studied ynamine umpolung chemistry (TL 34, 3311): 1. TMS2CuCNLi2 THF/HMPA, -23 C TMS E
2. Electrophile NPh- 92% - Himbert's push-pull ynamines can be ozonized to give 1,2,3-triones (Synthesis 1998, 1718):

O PhMeN R

O3, DCM, -50 C 42 - 93%

Ph O X

- and with propargylic alcohols (T 62, 3928)

O N Ph Alk

- Katrinsky created a homologation sequence for acid chlorides (OL 2, 3789):

O R R Cl N

PNBSA (0.1 eq) 80-85 C modest yields and de's
1. TsOH 2. -OH, TBAF 45 - 98%
2. [2 + 2] Cycloadditions 10% Tf2NH DCM, -35 C 74 - 90%
- Ynamines can be used to "enaminate" indoles at C3 (Y. Zhang, T 62, 3917)

- Enamines react with CO2 to give highly reactive ketene-amides (Ficini review)
- Internal capture can yield nitrogen heterocycles (Ficini Review)

O R2N O R1 R2N

O R1 O

NH2 CO2R

NR2 Alk

R2N O R1 R2N O

R1 R1 NR2
- Reaction with phosgene or thiophosgene yields a useful synthon (Ficini Review):
O Cl R2N R1 X Cl Cl R2N R1 Cl X
Nu: pyridines oxazoles etc.
- Similarly, reaction with ketones and LA give vinylamides (or imides, for ynamides):

R1 NR2 O

B - "Cycloadditions"
1. [2 + 1] Cycloadditions - Ynamines can react with Rhodium carbenoids to cyclopropenate (Pirrung, TL 35, 6229)
- This effectively accomplishes a 2-carbon homologation/functionalization of ketones Hsung recently applied this intramolecularly to ynamides and called it "yne-carbonyl metathesis" (OL 8, 231)

O N2 O

alkynyl pyrrole Rh(OAc)2

O N O O

n BF3OEt2 (cat) DCM, rt 33-88% ketones, heterocycles, maleimides tolerated

O O O N Ph

- Ynamides react with DMDO to make reactive oxirenes (Hsung, OL ASAP, DOI: ol703083k)
- Reactions with aryl isocyanates yield quinolones (Ficini Review, 1468)

O R2N NCO R1 N H R1

NR2 R1 N H O

favored in polar solvent

favored in non-polar solvent

O Ts N Ts N O H Ts N O

- Reactions with cyclohexenones achieve stereoselectivity with an equatorial methyl!
57% 89% 70% H Bn Bn Bn - Finally, two-carbon oxidative homologation of aldehydes (Hsung, OL 1, 1237)
80 - 100% trans - When reacted with cyclopentenone, selectivity of the R1 group is achieved:

O R O N Me H O N Me R O

LiOH 90%

>10 examples

1. DEAP 2. workup

O O H Me NEt2

O O H Me OH

O HO Me R

cat BF3OEt2 -78 to rt > 20:1 E:Z 58 - 91%
neutral or basic workup acidic workup - A tribute to MRL's demolished shin: Gold cycloisomerizations (Cossy, ACIEE 45, 6726)

3. [4 + 2] Cycloadditions - Much better than vinyl ketenes for making pyranes from MVK (Ficini Review)

TsN MeO2C

AuCl, DCM

O TsHN Me

> 95:5 dr!!

NEt2 O

NEt2 Me
65% among other examples MeO2C
- Complex bicyclic enamines are accessed easily (TL 1976 1025)

OH TsN Ph

AuCl, DCM 61% among other examples

CO2Me NEt2 Me

80 C - ethylene
- Ring expansions of cyclic imines (Viehe, ACIE 5, 585): - and pyridines: BF3OEt2

H3O+; NaBH4

Ph N NEt2 N NEt2 Ph N R O

NEt2 N R Ph Me H HO Me

- Nitro groups react readily with ynamines to give oxazoloisoxazoles (Nesi, T 55 13809)
- Pauson-Khand chemistry can be used on ynamides (Witulski ACIE 37, 489) Ts (OC)4Co Co(CO)4 alkene, TMANO Co2(CO)8 rt to 40 C Ts

N NO2 R

DEAP 52 - 63% R = H or Ester

N O R N O Me CONEt2

Ts N -stable under CO >95:5 dr Bn atm, chromatograhable

Ar N N Ar

DEAP rt 100%
- Boger studied DA's with tetrazines approaching Ningalin D and Purpurone(JOC 68, 3593)

O N N O

Ar NEt2 Me Ar

Zn, HOAc

Ar NEt2 Me

C - Functionalizations

- Ynamines can make kinetic anions:

R2N R2N X

BuLi or LHMDS

R2N R2N

X = R3Si or H
- "push-pull" ynamines react with hydrazines to give pyrazoles (Zakhartsova, IVVZKKT 41, 28)

Ar Me2N

H2N-NHR1 ? yield?
4. [3 + n] Cycloadditions - "click" like chemistry in 1963 (Huisgen, ACIE 2, 565)

NR1 N NMe2

O N3 Ph Et2N Ph

NEt2 O N N N Ph N N

2 eq n-BuLi E1 = BuI, DMF, TMSCl E2 = H or TMSCl -78 to rt 33 to 78%

R moderate selectivity

- Brandsma studied the bis-functionalization of ethynylpyrrole (Russ. JOC 32, 1164)
- similarly, nitrone 1,3-dipoles give isoxazolines (Viehe ACIE 5, 585)
OR. with E = elemental S, Se, or Te

Me O Ph N Ph

X = S, Se, or Te 45 - 49%

- Sn and Zn ynamines can be made and used in couplings (Helv. Chim. Acta 83, 641) ZnCl2 or ClSnBu3
- "push pull" ynamines can give isoxazoles and pyrazoles (Sukhova JOC 29, 1028 and 30, 49)

Pd(PPh3)4 THF

O R2N TMS

PhCNO or

- Bicyclic aniline derivs. were synthesized by Ranier and Imbriglio (JOC 65, 7272; OL 1, 2037)

O N Ph Ar O O N N Ar O

TMS PhMe, 100 C TsN TMS

Fe(CO)5,

TMS [O] then O TMS (H)

dienophile

O N Cl N H

TsN (H) TMS R1

(OC)3Fe

33 - 48%

- Witulski used yne-ynamines in [2+2+2] rxns do make indolines (Synlett 2000 1723)

NEt2 Ph TsN H

PhMe 54 - 70%

Grubb's or Wilkenson's

Grubbs selective for meta Wilk's selective for ortho 6
- Keteniminium PictetSpengler cyclization
V - Ynamines in Total Synthesis
1994 - Boger's synthesis of bleomycin A2 (JACS 116, 5619)
- Report #2 in a series - synthesis of the pyrimidine metal binding domain
2004 - Hsung - Desbromoarborescidines A and C (OL 7, 1047)

NMe H N N H

NTs 15% PNBSA

PhMe, 70 C 67% 4

NTs 8 steps

N H BnO

2006 - Cossy's HeckSuzukiMiyaura to lennoxamine (TL 47, 767)
Br OMe MeO CO2H O N N Br O
aq. NaOH, rt 100% 1. SOCl2, reflux 2. Et3N, DMAP, rt

OMe CO2H Br

OMe OMe
MeO OMe O CO2Et N EtO2C N N Bn2N

KHMDS, PhMe, then

CO2Et Me N N
1. NaBH4, EtOH, 5 C 6d, 70%

MeO Br

TfO I Ph

2. TBAF, 90%

MeO OMe O MeO Br H N
CO2Et dioxane, 101 C H2N 95 - 98%

2. TfOH, DCM; 75%

CO2Et Me NHBoc CONH2

2. MnO2, 83%

TfO O MeS

Sn O N O

B(OH)2 MeO OMe O MeO N Ar N MeO

1. H2, cat Pd/C (65%)

1. H2, cat Pd/C (80%) 2. H2SO4 (60%)
O N H2N Me Xc MeS N H2N Me O H N N N H2N CO2Et

NHBoc CONH2

98 - 100%
Pd(OAc)2 (5%) PPh3 (10%) 77%

H2N Me

THF, 0 C, 12h, 85%

OMe O MeO

OMe O N
1. Bu3SnH (89 - 95%) 2. NH3EtOH (80 - 85%) 3. LiOH (90 - 96%) 4. HClEtOAc (100%)

O H2N H N

NH2 N H2N N CO2H O

lennoxamine

 

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