New Enantioselective Synthesis of (10R,11S)-(+)-Juvenile Hormones I and II

Abstract

The (10R,11S)‐(+)‐juvenile hormones I (1) and II (2) were synthesized by Sharpless asymmetric dihydroxylations of methyl (2E,6E,10E)‐7‐ethyl‐3,11‐dimethyl‐2,6,10‐tridecatrienoate (4) and methyl (2E,6E,10E)‐3,7,11‐trimethyl‐2,6,10‐tridecatrienoate (5), respectively, as the key steps.

Transcription‐inducing activity of natural and synthetic juvenile hormone agonists through the Drosophila Methoprene‐tolerant protein

“…JH III also was prepared from MF according to the reported procedure . The physical and spectral properties of synthesized JH 0–III were in good agreement with those reported previously (see Section 1 of Supporting Information).…”

Transcription‐inducing activity of natural and synthetic juvenile hormone agonists through the Drosophila Methoprene‐tolerant protein

“…JH III also was prepared from MF according to the reported procedure . The physical and spectral properties of synthesized JH 0–III were in good agreement with those reported previously (see Section 1 of Supporting Information).…”

Establishment of “Ring-Size-Divergent” Synthetic Strategy: Divergent Synthesis, Stereochemical Assignments, and Biological Activity Studies of Nerolidol-Type Sesquiterpenoids and Feroniellins

“…The AE of 66 using Shi’s l -ketone 67 afforded monoepoxide 68 (94%, dr 85:15). The cyclization precursor 72 was synthesized in a four-step reaction sequence: (1) the bromination of a primary hydroxy group in 68 , (2) the dianion coupling reaction of bromide 69 with methyl acetoacetate, , (3) the conversion of β-ketoester 70 to enol phosphate 71 utilizing diethyl chlorophosphate and NaH, , and (4) the nucleophilic 1,4-addition/elimination reaction of 71 using a Gilman reagent. ,, THP 73 was produced at 73% yield through the exo -selective epoxide-opening cascade of 72 in H 2 O at 80 °C. − The reduction of an ester group in 73 afforded the desired THP-ringed nerolidol-type sesquiterpenoid 57 in 60% yield. The optical rotation of synthetic 57 , [α] D 24 +24.0 ( c 0.46, MeOH), corresponded to that of the natural product, [α] D 20 +28 ( c 1.0, MeOH) .…”

“…31 The AE of 66 using Shi's L-ketone 67 32 afforded monoepoxide 68 (94%, dr 85:15). The cyclization precursor 72 was synthesized in a four-step reaction sequence: (1) the bromination of a primary hydroxy group in 68, (2) the dianion coupling reaction of bromide 69 with methyl acetoacetate, 23j,33 (3) the conversion of β-ketoester 70 to enol phosphate 71 utilizing diethyl chlorophosphate and NaH, 33,34 and (4) the nucleophilic 1,4-addition/elimination reaction of 71 using a Gilman reagent. 23k,33,34 THP 73 was produced at 73% yield through the exo-selective epoxide-opening cascade of 72 in H 2 O at 80 °C.…”

Stereoselective Preparation and Reactions of Chiral Secondary Alkyllithiums

“…16 Deprotection of anti-78c with TBAF at 25 °C provided the pheromone (+)-lasiol (79) in 87% yield (dr 98:2, 99% ee). 22 Using analogous approaches, the total syntheses of (+)-13-norfaranal (80) (dr 97:3, 99% ee) 16,23 and (+)-faranal (81) (dr 97:3, 99% ee) 24 were achieved (Scheme 16). 16 Adding a ZnCl 2 solution to the chiral secondary alkylcopper reagents 70 led to mixed clusters, which displayed very high anti-S N 2′ regioselectivity.…”

Transcription‐inducing activity of natural and synthetic juvenile hormone agonists through the Drosophila Methoprene‐tolerant protein

“…JH III also was prepared from MF according to the reported procedure . The physical and spectral properties of synthesized JH 0–III were in good agreement with those reported previously (see Section 1 of Supporting Information).…”

Establishment of “Ring-Size-Divergent” Synthetic Strategy: Divergent Synthesis, Stereochemical Assignments, and Biological Activity Studies of Nerolidol-Type Sesquiterpenoids and Feroniellins

“…The AE of 66 using Shi’s l -ketone 67 afforded monoepoxide 68 (94%, dr 85:15). The cyclization precursor 72 was synthesized in a four-step reaction sequence: (1) the bromination of a primary hydroxy group in 68 , (2) the dianion coupling reaction of bromide 69 with methyl acetoacetate, , (3) the conversion of β-ketoester 70 to enol phosphate 71 utilizing diethyl chlorophosphate and NaH, , and (4) the nucleophilic 1,4-addition/elimination reaction of 71 using a Gilman reagent. ,, THP 73 was produced at 73% yield through the exo -selective epoxide-opening cascade of 72 in H 2 O at 80 °C. − The reduction of an ester group in 73 afforded the desired THP-ringed nerolidol-type sesquiterpenoid 57 in 60% yield. The optical rotation of synthetic 57 , [α] D 24 +24.0 ( c 0.46, MeOH), corresponded to that of the natural product, [α] D 20 +28 ( c 1.0, MeOH) .…”

“…31 The AE of 66 using Shi's L-ketone 67 32 afforded monoepoxide 68 (94%, dr 85:15). The cyclization precursor 72 was synthesized in a four-step reaction sequence: (1) the bromination of a primary hydroxy group in 68, (2) the dianion coupling reaction of bromide 69 with methyl acetoacetate, 23j,33 (3) the conversion of β-ketoester 70 to enol phosphate 71 utilizing diethyl chlorophosphate and NaH, 33,34 and (4) the nucleophilic 1,4-addition/elimination reaction of 71 using a Gilman reagent. 23k,33,34 THP 73 was produced at 73% yield through the exo-selective epoxide-opening cascade of 72 in H 2 O at 80 °C.…”

Stereoselective Preparation and Reactions of Chiral Secondary Alkyllithiums

“…16 Deprotection of anti-78c with TBAF at 25 °C provided the pheromone (+)-lasiol (79) in 87% yield (dr 98:2, 99% ee). 22 Using analogous approaches, the total syntheses of (+)-13-norfaranal (80) (dr 97:3, 99% ee) 16,23 and (+)-faranal (81) (dr 97:3, 99% ee) 24 were achieved (Scheme 16). 16 Adding a ZnCl 2 solution to the chiral secondary alkylcopper reagents 70 led to mixed clusters, which displayed very high anti-S N 2′ regioselectivity.…”

Transcription‐inducing activity of natural and synthetic juvenile hormone agonists through the Drosophila Methoprene‐tolerant protein

“…JH III also was prepared from MF according to the reported procedure . The physical and spectral properties of synthesized JH 0–III were in good agreement with those reported previously (see Section 1 of Supporting Information).…”

Establishment of “Ring-Size-Divergent” Synthetic Strategy: Divergent Synthesis, Stereochemical Assignments, and Biological Activity Studies of Nerolidol-Type Sesquiterpenoids and Feroniellins

“…The AE of 66 using Shi’s l -ketone 67 afforded monoepoxide 68 (94%, dr 85:15). The cyclization precursor 72 was synthesized in a four-step reaction sequence: (1) the bromination of a primary hydroxy group in 68 , (2) the dianion coupling reaction of bromide 69 with methyl acetoacetate, , (3) the conversion of β-ketoester 70 to enol phosphate 71 utilizing diethyl chlorophosphate and NaH, , and (4) the nucleophilic 1,4-addition/elimination reaction of 71 using a Gilman reagent. ,, THP 73 was produced at 73% yield through the exo -selective epoxide-opening cascade of 72 in H 2 O at 80 °C. − The reduction of an ester group in 73 afforded the desired THP-ringed nerolidol-type sesquiterpenoid 57 in 60% yield. The optical rotation of synthetic 57 , [α] D 24 +24.0 ( c 0.46, MeOH), corresponded to that of the natural product, [α] D 20 +28 ( c 1.0, MeOH) .…”

“…31 The AE of 66 using Shi's L-ketone 67 32 afforded monoepoxide 68 (94%, dr 85:15). The cyclization precursor 72 was synthesized in a four-step reaction sequence: (1) the bromination of a primary hydroxy group in 68, (2) the dianion coupling reaction of bromide 69 with methyl acetoacetate, 23j,33 (3) the conversion of β-ketoester 70 to enol phosphate 71 utilizing diethyl chlorophosphate and NaH, 33,34 and (4) the nucleophilic 1,4-addition/elimination reaction of 71 using a Gilman reagent. 23k,33,34 THP 73 was produced at 73% yield through the exo-selective epoxide-opening cascade of 72 in H 2 O at 80 °C.…”

Stereoselective Preparation and Reactions of Chiral Secondary Alkyllithiums

“…16 Deprotection of anti-78c with TBAF at 25 °C provided the pheromone (+)-lasiol (79) in 87% yield (dr 98:2, 99% ee). 22 Using analogous approaches, the total syntheses of (+)-13-norfaranal (80) (dr 97:3, 99% ee) 16,23 and (+)-faranal (81) (dr 97:3, 99% ee) 24 were achieved (Scheme 16). 16 Adding a ZnCl 2 solution to the chiral secondary alkylcopper reagents 70 led to mixed clusters, which displayed very high anti-S N 2′ regioselectivity.…”