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Московский государственный индустриальный университет

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Photochemistry_of_Organic

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					Retrosynthetic Photochemistry						457
Table 7.1 Three-membered rings
Key retrosynthetic step(s)									Reaction		Section
		hν							Di-p-methane		6.1.3
									rearrangement		6.1.3
									rearrangement
		hν							Oxa-di-p-methane		6.1.3
									Oxa-di-p-methane
			O						rearrangement
O			O						rearrangement
O
O		O
hν									Sigmatropic		6.1.6
									photorearrangement		6.1.6
									photorearrangement
		hν		O					a-Cleavage (Norrish		6.3.3
		- CO		O					type I reaction)		6.3.3
		- CO							type I reaction)
HO		OH	hν	O	H
		OH		O	H				Intramolecular
R											6.3.5
	R	R′		R		R′
									H-abstraction
R′									H-abstraction
R′
HS		SH	hν	S	H
		SH		S	H				Intramolecular
R											6.5.1
	R	R′		R		R′
									H-abstraction
R′									H-abstraction
R′
				hν					Photodecarboxylation		6.3.8
									Photodecarboxylation		6.3.8
			- CO2		O	O
						O
		R		hν	R	N	R	N2	Carbene photoformation;		6.4.2
R				R′ - N2		N	or		carbene addition		6.4.2
R′				R′ - N2		R′		R′
R′
O		O		hν		O			Photoelimination of N2	;
		O		hν		O			Photoelimination of N2	;	6.4.2
R N									nitrene addition		6.4.2
R N		R	N - N2		R	N3			nitrene addition
		R	N - N2		R	N3

458	Retrosynthetic Photochemistry
Table 7.2 Four-membered rings

Key retrosynthetic step(s)	Reaction	Section

hν

HO	R′	OH R′hν O H R′
R
	R	R
O	hν	O
		+

S	hν	S	+
			+
O O		1O	hν
		1O	3O
		2	2

sens

Photocycloaddition	6.1.5
	6.1.6
	6.3.7
Photocycloaddition	6.2.2
Photocycloaddition	6.1.5
Electrocyclic photorearrangement	6.1.2
Yang cyclization	6.3.5
	6.3.6
Oxetane formation	6.3.2
€	6.3.7
(Paterno`–Buchi reaction)	6.3.7
Thietane formation	6.5.1
Photooxygenation	6.7.2

Retrosynthetic Photochemistry		459
Table 7.3 Five-membered rings

Key retrosynthetic step(s)	Reaction	Section

	R′		R′		R′
R		OH X hν			H
R	X	OH X hν			O X
HO
X = O, CR2		R		R
X = O, CR2
			hν		H
		HS	hν		S
HS		HS			S
HS		R			R
R		R			R
O		LG	OH		LG	O
		LG			LG
	R		R	hν		R
			R			R

LG = leaving group

hν

Hal

	Intramolecular	6.3.5
	H-abstraction	6.3.5
	H-abstraction

Intramolecular	6.5.1
H-abstraction

Photoenolization 6.3.6

6.6.2

Photosubstitution

Hal = Cl, Br, I

460		Retrosynthetic Photochemistry
Table 7.4 Six-membered and larger rings

Key retrosynthetic step(s)		Reaction	Section

	hν	Electrocyclic	6.1.2
		photorearrangement	6.1.2
		photorearrangement

hν

2 Photocycloaddition 6.2.2 6.1.5

HO				HO	R1		R1	O
R1					R2	hν		R2	Photoenolization;	6.3.6
		R	2		R2	hν		R2	cycloaddition
		R							cycloaddition
	R'			R'		R'			Intramolecular	6.3.5
		X	OH	X	hν O H		X		Intramolecular	6.3.5
R		X	OH	X	hν O H		X		H-abstraction	6.4.4
			R		R				(various ring sizes)
X = 1 or more atoms
			hν						Electrocyclic	6.1.2
									photorearrangement
	R′	R		R′
		R
		N			R				Photoamination	6.4.4
		N	hν		R
			hν	H N
				H N					(various ring sizes)
									(various ring sizes)
	O			O		O
			base		hν				de Mayo reaction	6.1.6
							O		(various ring sizes)
				O LG			O
O				O LG			LG
LG = leaving group
		hν		hν					Beckmann	6.4.1
									Beckmann	6.4.1
N			O						photoisomerization
N		O
H					N
H			HN		N
					OH
N		Nu		N	N			N3
				N			hν
		NuH							Nitrene formation;	6.4.2
		NuH

									ring expansion

Nu = nucleophile

O	1O	hν
O	1O	3O
O		2 sens	2

Photooxygenation 6.7.2

		Retrosynthetic Photochemistry	461
Table 7.5 Condensed aromatic rings
Key retrosynthetic step(s)		Reaction	Section
oxidation	hν	Photoelectrocyclization;	6.1.2
		oxidation
		R

R hν

R [H]

Cycloaromatization 6.1.5 (photo-Bergman

reaction)

Table 7.6 Cage compounds

Key retrosynthetic step(s)			Reaction	Section
	hν		Photocycloaddition	6.1.5

	hν		Photorearrangement	6.2.1

	hν	+	Photocycloaddition	6.2.2

	hν		Photocycloaddition	6.2.2

O	hν	O
			Oxetane formation	6.3.2
		O

462			Retrosynthetic Photochemistry
Table 7.7		Spiro compounds
Key retrosynthetic step(s)			Reaction	Section
			O
		hν	Photoelectrocyclization	6.1.2
N O			Photoelectrocyclization	6.1.2
N O				6.4.1
R			N	6.4.1
			R
O	hν	O
O	hν	+
		+	Oxetane formation	6.3.2
			Oxetane formation	6.3.2
				6.3.7

Table 7.8 E-conﬁguration of a double bond

Key retrosynthetic step(s)			Reaction	Section

		hν	E Z photoisomerization	6.1.1
		hν
N	X

		N X	E Z photoisomerization	6.4.1

X = C, N

	Retrosynthetic Photochemistry	463
Table 7.9 C–C bond

Key retrosynthetic step(s)	Reaction	Section

sens*

[H]

hν

R''2NCH2R' R

R''2N

HO OH

hν

[H]

- CO

hν

- N2

hν

R S R'

-SO2 O O

hν

	h	LG
	h	+
		+
LG = leaving group		halogen, CN ...)
		hν
		Hal
		Hal = Cl, Br, I
		O
OH O	hν	O
		O

R	hν R	N
		N
R′	- N2	R′
O	R′	OH R′hν O H R′
+
R	R	R

Photocatalysed radical addition	6.8.1
Photochemical addition	6.1.4
via e and Hþ transfer	6.4.4
Pinacol formation	6.3.1
a-Cleavage (Norrish type I reaction)	6.3.3
Photoelimination of N2	6.4.1
	6.4.2
Photoelimination of SO2	6.5.2
Phototransposition	6.2.1
Photosubstitution	6.2.3
Photosubstitution	6.6.2
Photo-Fries rearrangement	6.3.8
Photoelimination of N2	6.4.2
Photoelimination of N2
Norrish type II elimination	6.3.4

464		Retrosynthetic Photochemistry
Table 7.10	C–O bonds

Key retrosynthetic step(s)		Reaction	Section

	hν
OR	ROH (H+)	Photoinduced nucleophile	6.1.4
R = H, alkyl		(often acid-catalysed) addition
R = H, alkyl

	OR		ea	[H];
	OR		ROH
			ROH
ea = electron acceptor
R	OR'		hν	R	Hal
R	OR'			R	Hal
		R'OH
R = alkyl, aryl
R' = H, alkyl; Hal = Cl, Br, I
	OH		hν			N2
			hν
			H2O
	O	ROH				hν		N2
					C O			N2
	OR					- N2		O
								O
R	OR'		hν	R S O R'
		- SO2			O O
		O		hν		LG
	NO					NO2
					LG = leaving group
R	ONO		hν		R NO2
R	ONO				R NO2
	O O					hν
					1O	hν	3O
					1O	2 sens	3O
						2 sens		2
O					1O	hν	3O
O					1O		3O	2
	O				2	sens		2
						sens
		CR2			CHR2		hν
		CR2					hν
						1O2		3O2
HOO							sens
HOO

Photoinduced (co-sensitized)	6.1.4
nucleophilic addition
Photosubstitution	6.2.3
	6.6.2
Photosubstitution	6.4.2
Ketene formation	6.4.2
Photoelimination of SO2	6.5.2
Intramolecular H-abstraction	6.4.3
Photorearrangement	6.4.3
Singlet oxygen formation and addition	6.7.2
Singlet oxygen formation	6.7.2
and endoperoxide formation
Singlet oxygen formation	6.7.3
and ene reaction

					Retrosynthetic Photochemistry	465
Table 7.11		C–N bonds
Key retrosynthetic step(s)					Reaction	Section
O	R'	H	O	hν	O	6.4.2
	R'				Nitrene formation and insertion	6.4.2
R	N	R	N	- N2 R	N3
	H
HO N
	CH		H3C
		hν	H3C		Barton reaction	6.4.2
		hν

	OH			ONO
	hν		hν		Beckmann photoisomerization	6.4.1
					Beckmann photoisomerization	6.4.1
N	O	O
H		O		N
H		HN		N
				OH
		hν		N
	N			N	Photoamination	6.4.4
	N			H	Photoamination	6.4.4
				H

Table 7.12 C–halogen atom bonds

Key retrosynthetic step(s)				Reaction	Section

		R-H	hν	Photohalogenation	6.6.1
R	Hal	2 Hal	Hal2

Hal = Cl, Br

Hal	hν
2 Hal	Hal2

Hal

Hal = Cl, Br

Photohalogenation

6.6.1

466	Retrosynthetic Photochemistry
Table 7.13 C–H, N–H bonds

Key retrosynthetic step(s)	Reaction	Section

OH	hν		O
H	[H]
H
	H	hν	N2
		hν

1.[e ]

2.[H]

H + CO2

hν

COO

H2O

hν

COOR'

H + CO2

+ MeOR'

MeOH

hν

C O

CH2 O

NR3

hν

NO2

[H]

hν

[H]

Hal

hν

Hal

[H]

Hal = Cl, Br

hν

Hal

NR3; [H]

Hal = Cl, Br

Photoreduction	6.3.1
Reduction of aryl diazonium salts	6.4.2
Photodecarboxylation	6.3.8
Ester photofragmentation	6.3.8
Photoreduction	6.4.4
Photoreduction	6.4.3
Photoreduction	6.6.2
Photoreduction	6.6.2
Photoreduction via

electron transfer	6.6.2

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